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Search for "enantioselective catalysis" in Full Text gives 31 result(s) in Beilstein Journal of Organic Chemistry.
Machine learning-guided strategies for reaction conditions design and optimization
- Lung-Yi Chen and
- Yi-Pei Li
Beilstein J. Org. Chem. 2024, 20, 2476–2492, doi:10.3762/bjoc.20.212
- are applicable to various substrates within the same reaction type [211][212][213][214][215]. For instance, the generality of chiral catalysts for asymmetric or enantioselective catalysis has been a longstanding interest in synthetic chemistry [216]. Angello et al. [53] applied uncertainty-minimizing
Graphical Abstract
Figure 1: Schematic diagram illustrating the data mining and preprocessing steps for chemical reaction datase...
Figure 2: A comparison of three types of reaction embedding methods: (A) descriptor-based, which use predefin...
Figure 3: A schematic diagram of how ML algorithms can be combined with HTE platforms to optimize reaction co...
Factors influencing the performance of organocatalysts immobilised on solid supports: A review
- Zsuzsanna Fehér,
- Dóra Richter,
- Gyula Dargó and
- József Kupai
Beilstein J. Org. Chem. 2024, 20, 2129–2142, doi:10.3762/bjoc.20.183
- organocatalyst also depend on the density of catalytic sites on the support surface, as well as the nature and length of the linker [8]. Additionally, the linker itself could serve as a competitive active site. In the case of enantioselective catalysis, the linker could promote the formation of racemic products
Graphical Abstract
Scheme 1: Esterification of oleic acid (1) with propylsulfonic acid (Pr-SO3H)-functionalised mesoporous silic...
Scheme 2: Using confinement of organocatalytic units for improving the enantioselectivity of silica-supported...
Scheme 3: Michael addition catalysed by cinchona thiourea immobilised on magnetic nanoparticles (13).
Scheme 4: Michael addition catalysed by cinchona thiourea in the presence of magnetic nanoparticles.
Scheme 5: Benzoin condensation catalysed by N-benzylthiazolium salt attached to mesoporous material.
Scheme 6: Photoinduced RAFT polymerisation of n-butyl acrylate (19) catalysed by silica nanoparticle-supporte...
Scheme 7: Pressure and temperature dependence of the 1,4-addition of propanal to trans-β-nitrostyrene under c...
Scheme 8: α-Amination of ethyl 2-oxocyclopentanecarboxylate catalysed by PS-THU which could be recycled over ...
Scheme 9: Preparation of supported catalysts C29–C31 from cinchona squaramides 29–31 modified with a primary ...
Scheme 10: Application of PGMA-supported organocatalysts C29–C31 in the asymmetric Michael addition of pentane...
Scheme 11: Alcoholytic desymmetrisation of a cyclic anhydride 34 catalysed by polyamide-supported cinchona sul...
Evaluation of the enantioselectivity of new chiral ligands based on imidazolidin-4-one derivatives
- Jan Bartáček,
- Karel Chlumský,
- Jan Mrkvička,
- Lucie Paloušová,
- Miloš Sedlák and
- Pavel Drabina
Beilstein J. Org. Chem. 2024, 20, 684–691, doi:10.3762/bjoc.20.62
- also tested in asymmetric aldol reactions. Under the optimised reaction conditions, aldol products with enantioselectivities of up to 91% ee were obtained. Keywords: asymmetric aldol reaction; asymmetric Henry reaction; chiral ligands; enantioselective catalysis; imidazolidine derivatives
- , chiral 2-(pyridin-2-yl)imidazolidin-4-one derivatives stand out as a prominent class of chiral nitrogen ligands in enantioselective catalysis. In this work, we focused on structurally modifying 2-(pyridin-2-yl)imidazolidin-4-one ligands to potentially expand the range of efficient catalysts. Our goal was
Graphical Abstract
Scheme 1: The preparation of 5-isopropyl-5-methyl-2-(pyridin-2-yl)imidazolidin-4-one derivatives and their ap...
Figure 1: The structure of newly designed ligands I–IV.
Figure 2: Plausible transition structures for the Henry reaction.
Switchable molecular tweezers: design and applications
- Pablo Msellem,
- Maksym Dekthiarenko,
- Nihal Hadj Seyd and
- Guillaume Vives
Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45
Graphical Abstract
Figure 1: Principle of switchable molecular tweezers.
Figure 2: Principle of pH-switchable molecular tweezers 1 [19].
Figure 3: a) pH-Switchable tweezers 2 substituted with alkyl chains as switchable lipids. b) Schematic depict...
Figure 4: Modification of spectral properties of 3 by controlled induction of Pt–Pt interactions.
Figure 5: Conformational switching of di(hydroxyphenyl)pyrimidine-based tweezer 4 upon alkylation or fluoride...
Figure 6: Hydrazone-based pH-responsive tweezers 5 for mesogenic modulation.
Figure 7: pH-Switchable molecular tweezers 6 bearing acridinium moieties.
Figure 8: a) Terpyridine and pyridine-hydrazone-pyridine analogs molecular tweezers and b) extended pyridine ...
Figure 9: Terpyridine-based molecular tweezers with M–salphen arms and their field of application. Figure 9 was adapt...
Figure 10: a) Terpyridine-based molecular tweezers for diphosphate recognition [48]; b) bishelicene chiroptical te...
Figure 11: Terpyridine-based molecular tweezers with allosteric cooperative binding.
Figure 12: Terpyridine-based molecular tweezers presenting closed by default conformation.
Figure 13: Pyridine-pyrimidine-pyridine-based molecular tweezers.
Figure 14: Coordination-responsive molecular tweezers based on nitrogen-containing ligands.
Figure 15: Molecular tweezers exploiting the remote bipyridine or pyridine binding to trigger the conformation...
Figure 16: Bipyridine-based molecular tweezers exploiting the direct s-trans to s-cis-switching for a) anion b...
Figure 17: a) Podand-based molecular tweezers [66,67]. b) Application of tweezers 32 for the catalytic allosteric reg...
Figure 18: Anion-triggered molecular tweezers based on calix[4]pyrrole.
Figure 19: Anion-triggered molecular tweezers.
Figure 20: a) Principle of the weak link approach (WLA) developed by Mirkin and its application to b) symmetri...
Figure 21: Molecular tweezers as allosteric catalyst in asymmetric epoxide opening [80].
Figure 22: Allosteric regulation of catalytic activity in ring-opening polymerization with double tweezers 41.
Figure 23: a) Conformational switching of 42 by intramolecular –S–S– bridge formation. b) Shift of conformatio...
Figure 24: a) Redox-active glycoluril-TTF tweezers 44. b) Mechanism of stepwise oxidation of said tweezers wit...
Figure 25: Mechanism of formation of the mixed-valence dimers of tweezers 45.
Figure 26: Mechanism of carbohydrate liberation upon redox-mediated conformation switching of 46.
Figure 27: a) The encapsulation properties of 47 as well as the DCTNF release process from its host–guest comp...
Figure 28: Redox-active bipyridinium-based tweezers. a) With a ferrocenyl hinge 49, b) with a propyl hinge 50 ...
Figure 29: Redox-active calix[4]arene porphyrin molecular tweezers.
Figure 30: a) Mechanism of the three orthogonal stimuli. b) Cubic scheme showing the eight different states of ...
Figure 31: Redox-controlled molecular gripper based on a diquinone resorcin[4]arene.
Figure 32: a) Shinkai's butterfly tweezers and their different host–guest properties depending on the isomer. ...
Figure 33: Cyclam-tethered tweezers and their different host–guest complexes depending on their configuration.
Figure 34: Azobenzene-based catalytic tweezers.
Figure 35: Photoswitchable PIEZO channel mimic.
Figure 36: Stilbene-based porphyrin tweezers for fullerene recognition.
Figure 37: Stiff-stilbene-based tweezers with urea or thiourea functional units for a) anion binding, b) anion...
Figure 38: Feringa’s photoswitchable organocatalyst (a) and different catalyzed reactions with that system (b)....
Figure 39: a) Irie and Takeshita’s thioindigo-based molecular tweezers. b) Family of hemithioindigo-based mole...
Figure 40: Dithienylethylene crown ether-bearing molecular tweezers reported by Irie and co-workers.
Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis
- Prodip Howlader and
- Michael Schmittel
Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62
- illustrates the opportunities in running enantioselective catalysis in mixed-ligand frameworks. Instead of constructing supramolecular catalysts by functionalization of the linker units, a different approach can be adopted where a catalytically active molecule is encapsulated inside a confined space, as
Graphical Abstract
Figure 1: Butterfly 1 (Figure was reprinted with permission from [45]. Copyright 2012 American Chemical Society. ...
Figure 2: Synthesis of the three-component heteroleptic molecular boat 8 and its use as a catalyst for the Kn...
Figure 3: Synthesis of the two-component triangle 14 and three-component heteroleptic prism 15 [59]. Figure was a...
Figure 4: Catalytic Michael addition reaction using the urea-decorated molecular prism 15 [59].
Figure 5: Self-assembly of two-component tetragonal prismatic architectures with different cavity size. Figur...
Figure 6: Construction of artificial LHS using rhodamine B as an acceptor and 24b as donor generating a photo...
Figure 7: Synthesis of supramolecular spheres with varying [AuCl] concentration inside the cavity. Figure was...
Figure 8: Hydroalkoxylation reaction of γ-allenol 34 in the presence of [AuCl]-encapsulated molecular spheres ...
Figure 9: Two-component heteroleptic triangles of different size containing a BINOL functionality. Figure was...
Figure 10: Asymmetric conjugate addition of chalcone 42 with trans-styrylboronic acid (43) catalyzed by BINOL-...
Figure 11: Encapsulation of monophosphoramidite-Rh(I) catalyst into a heteroleptic tetragonal prismatic cage 47...
Figure 12: (a) Representations of the basic HETPYP, HETPHEN, and HETTAP complex motifs. (b) The three-componen...
Figure 13: Two representative four-component rotors, with a (top) two-arm stator and (bottom) a four-arm stato...
Figure 14: Four-component rotors with a monohead rotator. Figure was adapted with permission from [94]. Copyright ...
Figure 15: (left) Click reaction catalyzed by rotors [Cu2(55)(60)(X)]2+. (right) Yield as a function of the ro...
Figure 16: A supramolecular AND gate. a) In truth table state (0,0) two nanoswitches serve as the receptor ens...
Figure 17: Two supramolecular double rotors (each has two rotational axes) and reference complex [Cu(78)]+ for...
Figure 18: The slider-on-deck system (82•X) (X = 83, 84, or 85). Figure is from [98] and was reprinted from the jo...
Figure 19: Catalysis of a conjugated addition reaction in the presence of the slider-on-deck system (82•X) (X ...
Figure 20: A rotating catalyst builds a catalytic machinery. For catalysis of the catalytic machinery, see Figure 21. F...
Figure 21: Catalytic machinery. Figure was adapted from [100] (“Evolution of catalytic machinery: three-component n...
Figure 22: An information system based on (re)shuffling components between supramolecular structures [99]. Figure ...
Figure 23: Switching between dimeric heteroleptic and homoleptic complex for OFF/ON catalytic formation of rot...
Figure 24: A chemically fueled catalytic system [112]. Figure was adapted from [112]. Copyright 2021 American Chemical S...
Figure 25: (Top) Operation of a fuel acid. (Bottom) Knoevenagel addition [112].
Figure 26: Development of the yield of Knoevenagel product 118 in a fueled system [112]. Figure was reprinted with ...
Figure 27: Weak-link strategy to increased catalytic activity in epoxide opening [119]. Figure was adapted from [24]. C...
Figure 28: A ON/OFF polymerization switch based on the weak-link approach [118]. Figure was reprinted with permissi...
Figure 29: A weak-link switch turning ON/OFF a Diels–Alder reaction [132]. Figure was reprinted with permission fro...
Figure 30: A catalyst duo allowing selective activation of one of two catalytic acylation reactions [133] upon subs...
Figure 31: A four-state switchable nanoswitch (redrawn from [134]).
Figure 32: Sequential catalysis as regulated by nanoswitch 138 and catalyst 139 in the presence of metal ions ...
Figure 33: Remote control of ON/OFF catalysis administrated by two nanoswitches through ion signaling (redrawn...
The asymmetric Henry reaction as synthetic tool for the preparation of the drugs linezolid and rivaroxaban
- Martin Vrbický,
- Karel Macek,
- Jaroslav Pochobradský,
- Jan Svoboda,
- Miloš Sedlák and
- Pavel Drabina
Beilstein J. Org. Chem. 2022, 18, 438–445, doi:10.3762/bjoc.18.46
- syntheses of these drugs were obtained in high yields and enantiomeric excesses of up to 91% ee. Keywords: asymmetric Henry reaction; enantioselective catalysis; linezolid; oxazolidine-2-one derivatives; rivaroxaban; Introduction Oxazolidine-2-one derivatives represent an important branch of
Graphical Abstract
Figure 1: The structure of the oxazolidine-2-one-containing drugs linezolid (1) and rivaroxaban (2).
Figure 2: Overview of the chiral ligands that were used for the study of the asymmetric Henry reaction.
Scheme 1: Syntheses of aldehydes 15–20.
Scheme 2: Synthesis of linezolid (1) and rivaroxaban (2) from nitroaldols 24 or 26.
Asymmetric organocatalytic Michael addition of cyclopentane-1,2-dione to alkylidene oxindole
- Estelle Silm,
- Ivar Järving and
- Tõnis Kanger
Beilstein J. Org. Chem. 2022, 18, 167–173, doi:10.3762/bjoc.18.18
- presence of a multifunctional squaramide catalyst. Michael adducts were obtained in high enantioselectivities and in moderate diastereoselectivities. Keywords: cyclopentane-1,2-dione; enantioselective catalysis; Michael addition; organocatalysis; squaramide; Introduction Diketones are generally very
Graphical Abstract
Figure 1: Model of the catalyst action.
Figure 2: Catalysts screened.
Scheme 1: Screening of different N-protecting groups. Reaction conditions: 0.2 M solution of 1 (1 equiv), 2 (...
Scheme 2: Scope of the reaction (the relative configuration of the major diastereoisomer is depicted). Reacti...
Scheme 3: Comparison reactions of E- and Z-isomers (the relative configurations of the major diastereoisomers...
Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds
- Alemayehu Gashaw Woldegiorgis and
- Xufeng Lin
Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185
- excellent enantioselectivity [31]. The widespread use of phosphoric acids and phosphates as chiral acids, chiral anions, and ligands is one of the most important achievements of modern enantioselective catalysis. The atropochiral BINOL, H8-BINOL and SPINOL [32] derived phosphoric acids (Figure 4) [33][34
Graphical Abstract
Figure 1: Representative examples of axially chiral biaryls, heterobiaryls, spiranes and allenes as ligands a...
Figure 2: Selected examples of axially chiral drugs and bioactive molecules.
Figure 3: Axially chiral functional materials and supramolecules.
Figure 4: Important chiral phosphoric acid scaffolds used in this review.
Scheme 1: Atroposelective aryl–aryl-bond formation by employing a facile [3,3]-sigmatropic rearrangement.
Scheme 2: Atroposelective synthesis of axially chiral biaryl amino alcohols 5.
Scheme 3: The enantioselective reaction of quinone and 2-naphthol derivatives.
Scheme 4: Enantioselective synthesis of multisubstituted biaryls.
Scheme 5: Enantioselective synthesis of axially chiral quinoline-derived biaryl atropisomers mediated by chir...
Scheme 6: Pd-Catalyzed atroposelective C–H olefination of biarylamines.
Scheme 7: Palladium-catalyzed directed atroposelective C–H allylation.
Scheme 8: Enantioselective synthesis of axially chiral (a) aryl indoles and (b) biaryldiols.
Scheme 9: Asymmetric arylation of indoles enabled by azo groups.
Scheme 10: Proposed mechanism for the asymmetric arylation of indoles.
Scheme 11: Enantioselective synthesis of axially chiral N-arylindoles [38].
Scheme 12: Enantioselective [3 + 2] formal cycloaddition and central-to-axial chirality conversion.
Scheme 13: Organocatalytic atroposelective arene functionalization of nitrosonaphthalene with indoles.
Scheme 14: Proposed reaction mechanism for the atroposelective arene functionalization of nitrosonaphthalenes.
Scheme 15: Asymmetric construction of axially chiral naphthylindoles [65].
Scheme 16: Enantioselective synthesis of axially chiral 3,3’-bisindoles [66].
Scheme 17: Atroposelective synthesis of 3,3’-bisiindoles bearing axial and central chirality.
Scheme 18: Enantioselective synthesis of axially chiral 3,3’-bisindoles bearing single axial chirality.
Scheme 19: Enantioselective reaction of azonaphthalenes with various pyrazolones.
Scheme 20: Enantioselective and atroposelective synthesis of axially chiral N-arylcarbazoles [73].
Scheme 21: Atroposelective cyclodehydration reaction.
Scheme 22: Atroposelective construction of axially chiral N-arylbenzimidazoles [78].
Scheme 23: Proposed reaction mechanism for the atroposelective synthesis of axially chiral N-arylbenzimidazole...
Scheme 24: Atroposelective synthesis of axially chiral arylpyrroles [21].
Scheme 25: Synthesis of axially chiral arylquinazolinones and its reaction pathway [35].
Scheme 26: Synthesis of axially chiral aryquinoline by Friedländer heteroannulation reaction and its proposed...
Scheme 27: Povarov cycloaddition–oxidative chirality conversion process.
Scheme 28: Atroposelective synthesis of oxindole-based axially chiral styrenes via kinetic resolution.
Scheme 29: Synthesis of axially chiral alkene-indole frame works [45].
Scheme 30: Proposed reaction mechanism for axially chiral alkene-indoles.
Scheme 31: Atroposelective C–H aminations of N-aryl-2-naphthylamines with azodicarboxylates.
Scheme 32: Synthesis of brominated atropisomeric N-arylquinoids.
Scheme 33: The enantioselective syntheses of axially chiral SPINOL derivatives.
Scheme 34: γ-Addition reaction of various 2,3-disubstituted indoles to β,γ-alkynyl-α-imino esters.
Scheme 35: Regio- and stereoselective γ-addition reactions of isoxazol-5(4H)-ones to β,γ-alkynyl-α-imino ester...
Scheme 36: Synthesis of chiral tetrasubstituted allenes and naphthopyrans.
Scheme 37: Asymmetric remote 1,8-conjugate additions of thiazolones and azlactones to propargyl alcohols.
Scheme 38: Synthesis of chiral allenes from 1-substituted 2-naphthols [107].
Enantioenriched α-substituted glutamates/pyroglutamates via enantioselective cyclopropenimine-catalyzed Michael addition of amino ester imines
- Zara M. Seibel,
- Jeffrey S. Bandar and
- Tristan H. Lambert
Beilstein J. Org. Chem. 2021, 17, 2077–2084, doi:10.3762/bjoc.17.134
- substitution is discussed. Compared to other methods, this protocol allows for a broader and more enantioselective access to pyroglutamate derivatives. Keywords: Brønsted base; cyclopropenimine; enantioselective catalysis; Michael addition; pyroglutamate; Introduction α-Substituted glutamates have value as
Graphical Abstract
Figure 1: Strategy for the synthesis of glutamate and pyroglutamate derivatives and several natural products ...
Figure 2: Effect of the aryl substituent on reaction efficiency and selectivity.
Figure 3: Proposed transition state model.
A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries
- Guido Gambacorta,
- James S. Sharley and
- Ian R. Baxendale
Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90
Graphical Abstract
Figure 1: Representative shares of the global F&F market (2018) segmented on their applications [1].
Figure 2: General structure of an international fragrance company [2].
Figure 3: The Michael Edwards fragrance wheel.
Figure 4: Examples of oriental (1–3), woody (4–7), fresh (8–10), and floral (11 and 12) notes.
Figure 5: A basic depiction of batch vs flow.
Scheme 1: Examples of reactions for which flow processing outperforms batch.
Scheme 2: Some industrially important aldol-based transformations.
Scheme 3: Biphasic continuous aldol reactions of acetone and various aldehydes.
Scheme 4: Aldol synthesis of 43 in flow using LiHMDS as the base.
Scheme 5: A semi-continuous synthesis of doravirine (49) involving a key aldol reaction.
Scheme 6: Enantioselective aldol reaction using 5-(pyrrolidin-2-yl)tetrazole (51) as catalyst in a microreact...
Scheme 7: Gröger's example of asymmetric aldol reaction in aqueous media.
Figure 6: Immobilised reagent column reactor types.
Scheme 8: Photoinduced thiol–ene coupling preparation of silica-supported 5-(pyrrolidin-2-yl)tetrazole 63 and...
Scheme 9: Continuous-flow approach for enantioselective aldol reactions using the supported catalyst 67.
Scheme 10: Ötvös’ employment of a solid-supported peptide aldol catalyst in flow.
Scheme 11: The use of proline tetrazole packed in a column for aldol reaction between cyclohexanone (65) and 2...
Scheme 12: Schematic diagram of an aminosilane-grafted Si-Zr-Ti/PAI-HF reactor for continuous-flow aldol and n...
Scheme 13: Continuous-flow condensation for the synthesis of the intermediate 76 to nabumetone (77) and Microi...
Scheme 14: Synthesis of ψ-Ionone (80) in continuous-flow via aldol condensation between citral (79) and aceton...
Scheme 15: Synthesis of β-methyl-ionones (83) from citral (79) in flow. The steps are separately described, an...
Scheme 16: Continuous-flow synthesis of 85 from 84 described by Gavriilidis et al.
Scheme 17: Continuous-flow scCO2 apparatus for the synthesis of 2-methylpentanal (87) and the self-condensed u...
Scheme 18: Chen’s two-step flow synthesis of coumarin (90).
Scheme 19: Pechmann condensation for the synthesis of 7-hydroxyxcoumarin (93) in flow. The setup extended to c...
Scheme 20: Synthesis of the dihydrojasmonate 35 exploiting nitro derivative proposed by Ballini et al.
Scheme 21: Silica-supported amines as heterogeneous catalyst for nitroaldol condensation in flow.
Scheme 22: Flow apparatus for the nitroaldol condensation of p-hydroxybenzaldehyde (102) to nitrostyrene 103 a...
Scheme 23: Nitroaldol reaction of 64 to 105 employing a quaternary ammonium functionalised PANF.
Scheme 24: Enantioselective nitroaldol condensation for the synthesis of 108 under flow conditions.
Scheme 25: Enatioselective synthesis of 1,2-aminoalcohol 110 via a copper-catalysed nitroaldol condensation.
Scheme 26: Examples of Knoevenagel condensations applied for fragrance components.
Scheme 27: Flow apparatus for Knoevenagel condensation described in 1989 by Venturello et al.
Scheme 28: Knoevenagel reaction using a coated multichannel membrane microreactor.
Scheme 29: Continuous-flow apparatus for Knoevenagel condensation employing sugar cane bagasse as support deve...
Scheme 30: Knoevenagel reaction for the synthesis of 131–135 in flow using an amine-functionalised silica gel. ...
Scheme 31: Continuous-flow synthesis of compound 137, a key intermediate for the synthesis of pregabalin (138)...
Scheme 32: Continuous solvent-free apparatus applied for the synthesis of compounds 140–143 using a TSE. Throu...
Scheme 33: Lewis et al. developed a spinning disc reactor for Darzens condensation of 144 and a ketone to furn...
Scheme 34: Some key industrial applications of conjugate additions in the F&F industry.
Scheme 35: Continuous-flow synthesis of 4-(2-hydroxyethyl)thiomorpholine 1,1-dioxide (156) via double conjugat...
Scheme 36: Continuous-flow system for Michael addition using CsF on alumina as the catalyst.
Scheme 37: Calcium chloride-catalysed asymmetric Michael addition using an immobilised chiral ligand.
Scheme 38: Continuous multistep synthesis for the preparation of (R)-rolipram (173). Si-NH2: primary amine-fun...
Scheme 39: Continuous-flow Michael addition using ion exchange resin Amberlyst® A26.
Scheme 40: Preparation of the heterogeneous catalyst 181 developed by Paixão et al. exploiting Ugi multicompon...
Scheme 41: Continuous-flow system developed by the Paixão’s group for the preparation of Michael asymmetric ad...
Scheme 42: Continuous-flow synthesis of nitroaldols catalysed by supported catalyst 184 developed by Wennemers...
Scheme 43: Heterogenous polystyrene-supported catalysts developed by Pericàs and co-workers.
Scheme 44: PANF-supported pyrrolidine catalyst for the conjugate addition of cyclohexanone (65) and trans-β-ni...
Scheme 45: Synthesis of (−)-paroxetine precursor 195 developed by Ötvös, Pericàs, and Kappe.
Scheme 46: Continuous-flow approach for the 5-step synthesis of (−)-oseltamivir (201) as devised by Hayashi an...
Scheme 47: Continuous-flow enzyme-catalysed Michael addition.
Scheme 48: Continuous-flow copper-catalysed 1,4 conjugate addition of Grignard reagents to enones. Reprinted w...
Scheme 49: A collection of commonly encountered hydrogenation reactions.
Figure 7: The ThalesNano H-Cube® continuous-flow hydrogenator.
Scheme 50: Chemoselective reduction of an α,β-unsaturated ketone using the H-Cube® reactor.
Scheme 51: Incorporation of Lindlar’s catalyst into the H-Cube® reactor for the reduction of an alkyne.
Scheme 52: Continuous-flow semi-hydrogenation of alkyne 208 to 209 using SACs with H-Cube® system.
Figure 8: The standard setups for tube-in-tube gas–liquid reactor units.
Scheme 53: Homogeneous hydrogenation of olefins using a tube-in-tube reactor setup.
Scheme 54: Recyclable heterogeneous flow hydrogenation system.
Scheme 55: Leadbeater’s reverse tube-in-tube hydrogenation system for olefin reductions.
Scheme 56: a) Hydrogenation using a Pd-immobilised microchannel reactor (MCR) and b) a representation of the i...
Scheme 57: Hydrogenation of alkyne 238 exploiting segmented flow in a Pd-immobilised capillary reactor.
Scheme 58: Continuous hydrogenation system for the preparation of cyrene (241) from (−)-levoglucosenone (240).
Scheme 59: Continuous hydrogenation system based on CSMs developed by Hornung et al.
Scheme 60: Chemoselective reduction of carbonyls (ketones over aldehydes) in flow.
Scheme 61: Continuous system for the semi-hydrogenation of 256 and 258, developed by Galarneau et al.
Scheme 62: Continuous synthesis of biodiesel fuel 261 from lignin-derived furfural acetone (260).
Scheme 63: Continuous synthesis of γ-valerolacetone (263) via CTH developed by Pineda et al.
Scheme 64: Continuous hydrogenation of lignin-derived biomass (products 265, 266, and 267) using a sustainable...
Scheme 65: Ru/C or Rh/C-catalysed hydrogenation of arene in flow as developed by Sajiki et al.
Scheme 66: Polysilane-immobilized Rh–Pt-catalysed hydrogenation of arenes in flow by Kobayashi et al.
Scheme 67: High-pressure in-line mixing of H2 for the asymmetric reduction of 278 at pilot scale with a 73 L p...
Figure 9: Picture of the PFR employed at Eli Lilly & Co. for the continuous hydrogenation of 278 [287]. Reprinted ...
Scheme 68: Continuous-flow asymmetric hydrogenation using Oppolzer's sultam 280 as chiral auxiliary.
Scheme 69: Some examples of industrially important oxidation reactions in the F&F industry. CFL: compact fluor...
Scheme 70: Gold-catalysed heterogeneous oxidation of alcohols in flow.
Scheme 71: Uozumi’s ARP-Pt flow oxidation protocol.
Scheme 72: High-throughput screening of aldehyde oxidation in flow using an in-line GC.
Scheme 73: Permanganate-mediated Nef oxidation of nitroalkanes in flow with the use of in-line sonication to p...
Scheme 74: Continuous-flow aerobic anti-Markovnikov Wacker oxidation.
Scheme 75: Continuous-flow oxidation of 2-benzylpyridine (312) using air as the oxidant.
Scheme 76: Continuous-flow photo-oxygenation of monoterpenes.
Scheme 77: A tubular reactor design for flow photo-oxygenation.
Scheme 78: Glucose oxidase (GOx)-mediated continuous oxidation of glucose using compressed air and the FFMR re...
Scheme 79: Schematic continuous-flow sodium hypochlorite/TEMPO oxidation of alcohols.
Scheme 80: Oxidation using immobilised TEMPO (344) was developed by McQuade et al.
Scheme 81: General protocol for the bleach/catalytic TBAB oxidation of aldehydes and alcohols.
Scheme 82: Continuous-flow PTC-assisted oxidation using hydrogen peroxide. The process was easily scaled up by...
Scheme 83: Continuous-flow epoxidation of cyclohexene (348) and in situ preparation of m-CPBA.
Scheme 84: Continuous-flow epoxidation using DMDO as oxidant.
Scheme 85: Mukayama aerobic epoxidation optimised in flow mode by the Favre-Réguillon group.
Scheme 86: Continuous-flow asymmetric epoxidation of derivatives of 359 exploiting a biomimetic iron catalyst.
Scheme 87: Continuous-flow enzymatic epoxidation of alkenes developed by Watts et al.
Scheme 88: Engineered multichannel microreactor for continuous-flow ozonolysis of 366.
Scheme 89: Continuous-flow synthesis of the vitamin D precursor 368 using multichannel microreactors. MFC: mas...
Scheme 90: Continuous ozonolysis setup used by Kappe et al. for the synthesis of various substrates employing ...
Scheme 91: Continuous-flow apparatus for ozonolysis as developed by Ley et al.
Scheme 92: Continuous-flow ozonolysis for synthesis of vanillin (2) using a film-shear flow reactor.
Scheme 93: Examples of preparative methods for ajoene (386) and allicin (388).
Scheme 94: Continuous-flow oxidation of thioanisole (389) using styrene-based polymer-supported peroxytungstat...
Scheme 95: Continuous oxidation of thiosulfinates using Oxone®-packed reactor.
Scheme 96: Continuous-flow electrochemical oxidation of thioethers.
Scheme 97: Continuous-flow oxidation of 400 to cinnamophenone (235).
Scheme 98: Continuous-flow synthesis of dehydrated material 401 via oxidation of methyl dihydrojasmonate (33).
Scheme 99: Some industrially important transformations involving Grignard reagents.
Scheme 100: Grachev et al. apparatus for continuous preparation of Grignard reagents.
Scheme 101: Example of fluidized Mg bed reactor with NMR spectrometer as on-line monitoring system.
Scheme 102: Continuous-flow synthesis of Grignard reagents and subsequent quenching reaction.
Figure 10: Membrane-based, liquid–liquid separator with integrated pressure control [52]. Adapted with permission ...
Scheme 103: Continuous-flow synthesis of 458, an intermediate to fluconazole (459).
Scheme 104: Continuous-flow synthesis of ketones starting from benzoyl chlorides.
Scheme 105: A Grignard alkylation combining CSTR and PFR technologies with in-line infrared reaction monitoring....
Scheme 106: Continuous-flow preparation of 469 from Grignard addition of methylmagnesium bromide.
Scheme 107: Continuous-flow synthesis of Grignard reagents 471.
Scheme 108: Preparation of the Grignard reagent 471 using CSTR and the continuous process for synthesis of the ...
Scheme 109: Continuous process for carboxylation of Grignard reagents in flow using tube-in-tube technology.
Scheme 110: Continuous synthesis of propargylic alcohols via ethynyl-Grignard reagent.
Scheme 111: Silica-supported catalysed enantioselective arylation of aldehydes using Grignard reagents in flow ...
Scheme 112: Acid-catalysed rearrangement of citral and dehydrolinalool derivatives.
Scheme 113: Continuous stilbene isomerisation with continuous recycling of photoredox catalyst.
Scheme 114: Continuous-flow synthesis of compound 494 as developed by Ley et al.
Scheme 115: Selected industrial applications of DA reaction.
Scheme 116: Multistep flow synthesis of the spirocyclic structure 505 via employing DA cycloaddition.
Scheme 117: Continuous-flow DA reaction developed in a plater flow reactor for the preparation of the adduct 508...
Scheme 118: Continuous-flow DA reaction using a silica-supported imidazolidinone organocatalyst.
Scheme 119: Batch vs flow for the DA reaction of (cyclohexa-1,5-dien-1-yloxy)trimethylsilane (513) with acrylon...
Scheme 120: Continuous-flow DA reaction between 510 and 515 using a shell-core droplet system.
Scheme 121: Continuous-flow synthesis of bicyclic systems from benzyne precursors.
Scheme 122: Continuous-flow synthesis of bicyclic scaffolds 527 and 528 for further development of potential ph...
Scheme 123: Continuous-flow inverse-electron hetero-DA reaction to pyridine derivatives such as 531.
Scheme 124: Comparison between batch and flow for the synthesis of pyrimidinones 532–536 via retro-DA reaction ...
Scheme 125: Continuous-flow coupled with ultrasonic system for preparation of ʟ-ascorbic acid derivatives 539 d...
Scheme 126: Two-step continuous-flow synthesis of triazole 543.
Scheme 127: Continuous-flow preparation of triazoles via CuAAC employing 546-based heterogeneous catalyst.
Scheme 128: Continuous-flow synthesis of compounds 558 through A3-coupling and 560 via AgAAC both employing the...
Scheme 129: Continuous-flow photoinduced [2 + 2] cycloaddition for the preparation of bicyclic derivatives of 5...
Scheme 130: Continuous-flow [2 + 2] and [5 + 2] cycloaddition on large scale employing a flow reactor developed...
Scheme 131: Continuous-flow preparation of the tricyclic structures 573 and 574 starting from pyrrole 570 via [...
Scheme 132: Continuous-flow [2 + 2] photocyclization of cinnamates.
Scheme 133: Continuous-flow preparation of cyclobutane 580 on a 5-plates photoreactor.
Scheme 134: Continuous-flow [2 + 2] photocycloaddition under white LED lamp using heterogeneous PCN as photocat...
Figure 11: Picture of the parallel tube flow reactor (PTFR) "The Firefly" developed by Booker-Milburn et al. a...
Scheme 135: Continuous-flow acid-catalysed [2 + 2] cycloaddition between silyl enol ethers and acrylic esters.
Scheme 136: Continuous synthesis of lactam 602 using glass column reactors.
Scheme 137: In situ generation of ketenes for the Staudinger lactam synthesis developed by Ley and Hafner.
Scheme 138: Application of [2 + 2 + 2] cycloadditions in flow employed by Ley et al.
Scheme 139: Examples of FC reactions applied in F&F industry.
Scheme 140: Continuous-flow synthesis of ibuprofen developed by McQuade et al.
Scheme 141: The FC acylation step of Jamison’s three-step ibuprofen synthesis.
Scheme 142: Synthesis of naphthalene derivative 629 via FC acylation in microreactors.
Scheme 143: Flow system for rapid screening of catalysts and reaction conditions developed by Weber et al.
Scheme 144: Continuous-flow system developed by Buorne, Muller et al. for DSD optimisation of the FC acylation ...
Scheme 145: Continuous-flow FC acylation of alkynes to yield β-chlorovinyl ketones such as 638.
Scheme 146: Continuous-flow synthesis of tonalide (619) developed by Wang et al.
Scheme 147: Continuous-flow preparation of acylated arene such as 290 employing Zr4+-β-zeolite developed by Kob...
Scheme 148: Flow system applied on an Aza-FC reaction catalysed by the thiourea catalyst 648.
Scheme 149: Continuous hydroformylation in scCO2.
Scheme 150: Two-step flow synthesis of aldehyde 655 through a sequential Heck reaction and subsequent hydroform...
Scheme 151: Single-droplet (above) and continuous (below) flow reactors developed by Abolhasani et al. for the ...
Scheme 152: Continuous hydroformylation of 1-dodecene (655) using a PFR-CSTR system developed by Sundmacher et ...
Scheme 153: Continuous-flow synthesis of the aldehyde 660 developed by Eli Lilly & Co. [32]. Adapted with permissio...
Scheme 154: Continuous asymmetric hydroformylation employing heterogenous catalst supported on carbon-based sup...
Scheme 155: Examples of acetylation in F&F industry: synthesis of bornyl (S,R,S-664) and isobornyl (S,S,S-664) ...
Scheme 156: Continuous-flow preparation of bornyl acetate (S,R,S-664) employing the oscillating flow reactor.
Scheme 157: Continuous-flow synthesis of geranyl acetate (666) from acetylation of geraniol (343) developed by ...
Scheme 158: 12-Ttungstosilicic acid-supported silica monolith-catalysed acetylation in flow.
Scheme 159: Continuous-flow preparation of cyclopentenone 676.
Scheme 160: Two-stage synthesis of coumarin (90) via acetylation of salicylaldehyde (88).
Scheme 161: Intensification process for acetylation of 5-methoxytryptamine (677) to melatonin (678) developed b...
Scheme 162: Examples of macrocyclic musky odorants both natural (679–681) and synthetic (682 and 683).
Scheme 163: Flow setup combined with microwave for the synthesis of macrocycle 686 via RCM.
Scheme 164: Continuous synthesis of 2,5-dihydro-1H-pyrroles via ring-closing metathesis.
Scheme 165: Continuous-flow metathesis of 485 developed by Leadbeater et al.
Figure 12: Comparison between RCM performed using different routes for the preparation of 696. On the left the...
Scheme 166: Continuous-flow RCM of 697 employed the solid-supported catalyst 698 developed by Grela, Kirschning...
Scheme 167: Continuous-flow RORCM of cyclooctene employing the silica-absorbed catalyst 700.
Scheme 168: Continuous-flow self-metathesis of methyl oleate (703) employing SILP catalyst 704.
Scheme 169: Flow apparatus for the RCM of 697 using a nanofiltration membrane for the recovery and reuse of the...
Scheme 170: Comparison of loadings between RCMs performed with different routes for the synthesis of 709.
Recent advances in palladium-catalysed asymmetric 1,4–additions of arylboronic acids to conjugated enones and chromones
- Jan Bartáček,
- Jan Svoboda,
- Martin Kocúrik,
- Jaroslav Pochobradský,
- Alexander Čegan,
- Miloš Sedlák and
- Jiří Váňa
Beilstein J. Org. Chem. 2021, 17, 1048–1085, doi:10.3762/bjoc.17.84
- given combination of enone and arylboronic acid. Keywords: asymmetric reaction; boronic acid; conjugated enones; chromones; enantioselective catalysis; Michael addition; Pd complexes; Introduction The asymmetric 1,4-addition of arylboronic acids to conjugated cyclic enones and chromones is a very
Graphical Abstract
Scheme 1: Synthesis of optically pure 4-phenylchroman-2-one [34].
Scheme 2: Synthesis of (R)-tolterodine [3].
Scheme 3: Catalytic cycle of the Pd(II)-catalysed 1,4-addition of organoboron reagents to enones [3,26,35].
Scheme 4: Enantioselective β-arylation of cyclohexanone [38].
Scheme 5: Application of L2/Pd(OAc)2 in the total synthesis of terpenes [8].
Scheme 6: Plausible catalytic cycle for the addition of phenylboronic acid to 2-cyclohexenone catalysed by L3...
Scheme 7: Microwave-assisted addition of phenylboronic acid to 2-cyclohexenone catalysed by L4/Pd2(dba)3·CHCl3...
Scheme 8: Plausible catalytic cycle of the addition of phenylboronic acid to 2-cyclohexenone catalysed by pal...
Scheme 9: Proposed catalytic cycle for the addition of phenylboronic acids to 2-cyclohexenone catalysed by Pd...
Scheme 10: Usage of addition reactions of boronic acids to various chromones in the syntheses of potentially a...
Scheme 11: Multigram-scale synthesis of ABBV-2222 [6].
Scheme 12: Application of the asymmetric addition of phenylboronic acid to a chromone derivative for the total...
Scheme 13: Plausible catalytic cycle for the addition of phenylboronic acid to 3-methyl-2-cyclohexenone cataly...
Scheme 14: Total syntheses of naturally occurring terpenoids [10,11].
Scheme 15: Use of the L9/Pd(TFA)2 catalytic system for the synthesis of intermediates of biologically active c...
Scheme 16: Usage of a Michael addition catalysed by L9/Pd(TFA)2 in the total synthesis of (–)-ar-tenuifolene [12].
Scheme 17: Synthesis of terpenoids by Michael addition to 3-methyl-2-cyclopentenone [13].
Scheme 18: Rh-catalysed isomerisation of 3-alkyl-3-arylcyclopentanones to 1-tetralones [53].
Scheme 19: Addition reaction of phenylboronic acid to 3-methyl-2-cyclohexenone catalysed by L9/Pd(TFA)2 in wat...
Scheme 20: Micellar nanoreactor PdL10c for the synthesis of flavanones [58].
Scheme 21: Plausible catalytic cycle for the desymmetrisation of polycyclic cyclohexenediones by the addition ...
Scheme 22: Attempt to use the catalytic system L2/Pd(TFA)2 for the addition of phenylboronic acid to 3-methyl-...
Scheme 23: Ring opening of an enantioenriched tetrahydropyran-2-one derivative as alternative strategy to line...
Scheme 24: Synthesis of biologically active compounds from addition products [14-16].
Scheme 25: Chiral 1,10-phenantroline derivative L15 as ligand for the Pd-catalysed addition reactions of pheny...
Scheme 26: The Rh-catalysed addition reaction of phenylboronic acid to a 3-substituted enone [20].
Scheme 27: Underdeveloped methodologies [14,15,65-67].
Scheme 28: Flowchart for the selection of the proper catalytic system.
Palladium nanoparticles supported on chitin-based nanomaterials as heterogeneous catalysts for the Heck coupling reaction
- Tony Jin,
- Malickah Hicks,
- Davis Kurdyla,
- Sabahudin Hrapovic,
- Edmond Lam and
- Audrey Moores
Beilstein J. Org. Chem. 2020, 16, 2477–2483, doi:10.3762/bjoc.16.201
- transformations [7][8][9]. Furthermore, the chiral nature of polysaccharides has also been used as a tool for enantioselective catalysis such as carbonyl hydrogenations and amino acid hydrolysis, proving the unique ability of these biomass-based supports [10][11]. Chitin is another type of biomass feedstock that
Graphical Abstract
Scheme 1: Pathway for the formation of ChNC and subsequently ChsNCs from bulk chitin.
Figure 1: TEM micrographs of (a) ChNCs and (b) ChsNCs. Both samples were stained and prepared on glow-dischar...
Scheme 2: Catalyst fabrication method for the deposition of Pd NPs onto chitin (PdNP@ChNC) and chitosan (PdNP...
Figure 2: TEM micrographs of (a) PdNP@ChNCs and (b) PdNP@ChsNCs. The samples were placed on glow discharged T...
Figure 3: High-resolution X-ray photoelectron spectroscopy of the Pd 3d region of (a) PdNP@ChNC and (b) PdNP@...
Recent developments in enantioselective photocatalysis
- Callum Prentice,
- James Morrisson,
- Andrew D. Smith and
- Eli Zysman-Colman
Beilstein J. Org. Chem. 2020, 16, 2363–2441, doi:10.3762/bjoc.16.197
- Kingdom 10.3762/bjoc.16.197 Abstract Enantioselective photocatalysis has rapidly grown into a powerful tool for synthetic chemists. This review describes the various strategies for creating enantioenriched products through merging enantioselective catalysis and photocatalysis, with a focus on the most
- ; photocatalysis; photochemistry; Introduction Enantioselective catalysis has become a central focus for organic synthetic chemistry, particularly since the Nobel prize was awarded to Sharpless, Knowles, and Noyori for their pioneering work in the field. In the last 15 years, photocatalysis has become a
- photocatalysts (PCs) generate excited state substrates that can then undergo reactions that would be impossible in the ground state [4]. A challenge for enantioselective catalysis is stifling the racemic background reaction, which is generally achieved through a lower activation energy for the catalysed process
Graphical Abstract
Scheme 1: Amine/photoredox-catalysed α-alkylation of aldehydes with alkyl bromides bearing electron-withdrawi...
Scheme 2: Amine/HAT/photoredox-catalysed α-functionalisation of aldehydes using alkenes.
Scheme 3: Amine/cobalt/photoredox-catalysed α-functionalisation of ketones and THIQs.
Scheme 4: Amine/photoredox-catalysed α-functionalisation of aldehydes or ketones with imines. (a) Using keton...
Scheme 5: Bifunctional amine/photoredox-catalysed enantioselective α-functionalisation of aldehydes.
Scheme 6: Bifunctional amine/photoredox-catalysed α-functionalisation of aldehydes using amine catalysts via ...
Scheme 7: Amine/photoredox-catalysed RCA of iminium ion intermediates. (a) Synthesis of quaternary stereocent...
Scheme 8: Bifunctional amine/photoredox-catalysed RCA of enones in a radical chain reaction initiated by an i...
Scheme 9: Bifunctional amine/photoredox-catalysed RCA reactions of iminium ions with different radical precur...
Scheme 10: Bifunctional amine/photoredox-catalysed radical cascade reactions between enones and alkenes with a...
Scheme 11: Amine/photocatalysed photocycloadditions of iminium ion intermediates. (a) External photocatalyst u...
Scheme 12: Amine/photoredox-catalysed addition of acrolein (94) to iminium ions.
Scheme 13: Dual NHC/photoredox-catalysed acylation of THIQs.
Scheme 14: NHC/photocatalysed spirocyclisation via photoisomerisation of an extended Breslow intermediate.
Scheme 15: CPA/photoredox-catalysed aza-pinacol cyclisation.
Scheme 16: CPA/photoredox-catalysed Minisci-type reaction between azaarenes and α-amino radicals.
Scheme 17: CPA/photoredox-catalysed radical additions to azaarenes. (a) α-Amino radical or ketyl radical addit...
Scheme 18: CPA/photoredox-catalysed reduction of azaarene-derived substrates. (a) Reduction of ketones. (b) Ex...
Scheme 19: CPA/photoredox-catalysed radical coupling reactions of α-amino radicals with α-carbonyl radicals. (...
Scheme 20: CPA/photoredox-catalysed Povarov reaction.
Scheme 21: CPA/photoredox-catalysed reactions with imines. (a) Decarboxylative imine generation followed by Po...
Scheme 22: Bifunctional CPA/photocatalysed [2 + 2] photocycloadditions.
Scheme 23: PTC/photocatalysed oxygenation of 1-indanone-derived β-keto esters.
Scheme 24: PTC/photoredox-catalysed perfluoroalkylation of 1-indanone-derived β-keto esters via a radical chai...
Scheme 25: Bifunctional hydrogen bonding/photocatalysed intramolecular [2 + 2] photocycloadditions of quinolon...
Scheme 26: Bifunctional hydrogen bonding/photocatalysed intramolecular RCA cyclisation of a quinolone.
Scheme 27: Bifunctional hydrogen bonding/photocatalysed intramolecular [2 + 2] photocycloadditions of quinolon...
Scheme 28: Bifunctional hydrogen bonding/photocatalysed [2 + 2] photocycloaddition reactions. (a) First use of...
Scheme 29: Bifunctional hydrogen bonding/photocatalysed deracemisation of allenes.
Scheme 30: Bifunctional hydrogen bonding/photocatalysed deracemisation reactions. (a) Deracemisation of sulfox...
Scheme 31: Bifunctional hydrogen bonding/photocatalysed intramolecular [2 + 2] photocycloaddition of coumarins....
Scheme 32: Bifunctional hydrogen bonding/photocatalysed [2 + 2] photocycloadditions of quinolones. (a) Intramo...
Scheme 33: Hydrogen bonding/photocatalysed formal arylation of benzofuranones.
Scheme 34: Hydrogen bonding/photoredox-catalysed dehalogenative protonation of α,α-chlorofluoro ketones.
Scheme 35: Hydrogen bonding/photoredox-catalysed reductions. (a) Reduction of 1,2-diketones. (b) Reduction of ...
Scheme 36: Hydrogen bonding/HAT/photocatalysed deracemisation of cyclic ureas.
Scheme 37: Hydrogen bonding/HAT/photoredox-catalysed synthesis of cyclic sulfonamides.
Scheme 38: Hydrogen bonding/photoredox-catalysed reaction between imines and indoles.
Scheme 39: Chiral cation/photoredox-catalysed radical coupling of two α-amino radicals.
Scheme 40: Chiral phosphate/photoredox-catalysed hydroetherfication of alkenols.
Scheme 41: Chiral phosphate/photoredox-catalysed synthesis of pyrroloindolines.
Scheme 42: Chiral anion/photoredox-catalysed radical cation Diels–Alder reaction.
Scheme 43: Lewis acid/photoredox-catalysed cycloadditions of carbonyls. (a) Formal [2 + 2] cycloaddition of en...
Scheme 44: Lewis acid/photoredox-catalysed RCA reaction using a scandium Lewis acid between α-amino radicals a...
Scheme 45: Lewis acid/photoredox-catalysed RCA reaction using a copper Lewis acid between α-amino radicals and...
Scheme 46: Lewis acid/photoredox-catalysed synthesis of 1,2-amino alcohols from aldehydes and nitrones using a...
Scheme 47: Lewis acid/photocatalysed [2 + 2] photocycloadditions of enones and alkenes.
Scheme 48: Meggers’s chiral-at-metal catalysts.
Scheme 49: Lewis acid/photoredox-catalysed α-functionalisation of ketones with alkyl bromides bearing electron...
Scheme 50: Bifunctional Lewis acid/photoredox-catalysed radical coupling reaction using α-chloroketones and α-...
Scheme 51: Lewis acid/photocatalysed RCA of enones. (a) Using aldehydes as acyl radical precursors. (b) Other ...
Scheme 52: Bifunctional Lewis acid/photocatalysis for a photocycloaddition of enones.
Scheme 53: Lewis acid/photoredox-catalysed RCA reactions of enones using DHPs as radical precursors.
Scheme 54: Lewis acid/photoredox-catalysed functionalisation of β-ketoesters. (a) Hydroxylation reaction catal...
Scheme 55: Bifunctional copper-photocatalysed alkylation of imines.
Scheme 56: Copper/photocatalysed alkylation of imines. (a) Bifunctional copper catalysis using α-silyl amines....
Scheme 57: Bifunctional Lewis acid/photocatalysed intramolecular [2 + 2] photocycloaddition.
Scheme 58: Bifunctional Lewis acid/photocatalysed [2 + 2] photocycloadditions (a) Intramolecular cycloaddition...
Scheme 59: Bifunctional Lewis acid/photocatalysed rearrangement of 2,4-dieneones.
Scheme 60: Lewis acid/photocatalysed [2 + 2] cycloadditions of cinnamate esters and styrenes.
Scheme 61: Nickel/photoredox-catalysed arylation of α-amino acids using aryl bromides.
Scheme 62: Nickel/photoredox catalysis. (a) Desymmetrisation of cyclic meso-anhydrides using benzyl trifluorob...
Scheme 63: Nickel/photoredox catalysis for the acyl-carbamoylation of alkenes with aldehydes using TBADT as a ...
Scheme 64: Bifunctional copper/photoredox-catalysed C–N coupling between α-chloro amides and carbazoles or ind...
Scheme 65: Bifunctional copper/photoredox-catalysed difunctionalisation of alkenes with alkynes and alkyl or a...
Scheme 66: Copper/photoredox-catalysed decarboxylative cyanation of benzyl phthalimide esters.
Scheme 67: Copper/photoredox-catalysed cyanation reactions using TMSCN. (a) Propargylic cyanation (b) Ring ope...
Scheme 68: Palladium/photoredox-catalysed allylic alkylation reactions. (a) Using alkyl DHPs as radical precur...
Scheme 69: Manganese/photoredox-catalysed epoxidation of terminal alkenes.
Scheme 70: Chromium/photoredox-catalysed allylation of aldehydes.
Scheme 71: Enzyme/photoredox-catalysed dehalogenation of halolactones.
Scheme 72: Enzyme/photoredox-catalysed dehalogenative cyclisation.
Scheme 73: Enzyme/photoredox-catalysed reduction of cyclic imines.
Scheme 74: Enzyme/photocatalysed enantioselective reduction of electron-deficient alkenes as mixtures of (E)/(Z...
Scheme 75: Enzyme/photoredox catalysis. (a) Deacetoxylation of cyclic ketones. (b) Reduction of heteroaromatic...
Scheme 76: Enzyme/photoredox-catalysed synthesis of indole-3-ones from 2-arylindoles.
Scheme 77: Enzyme/HAT/photoredox catalysis for the DKR of primary amines.
Scheme 78: Bifunctional enzyme/photoredox-catalysed benzylic C–H hydroxylation of trifluoromethylated arenes.
NHC-catalyzed enantioselective synthesis of β-trifluoromethyl-β-hydroxyamides
- Alyn T. Davies,
- Mark D. Greenhalgh,
- Alexandra M. Z. Slawin and
- Andrew D. Smith
Beilstein J. Org. Chem. 2020, 16, 1572–1578, doi:10.3762/bjoc.16.129
- moderate to good yield as a single diastereoisomer. Keywords: enantioselective catalysis; formal [2 + 2] cycloaddition; N-heterocyclic carbene; ring opening; trifluoromethyl group; Introduction The trifluoromethyl unit holds a prominent and privileged position within organic chemistry [1][2][3][4][5][6
Graphical Abstract
Figure 1: Organocatalytic enantioselective aldol approaches using trifluoroacetophenone derivatives.
Figure 2: NHC-catalyzed approaches to β-lactones using trifluoroacetophenone derivatives.
Scheme 1: Reaction scope with respect to the nucleophile. aIsolated yield of the product in >95:5 dr. bDeterm...
Scheme 2: Reaction scope with respect to the trifluoroacetophenone derivative and α-aroyloxyaldehyde. aIsolat...
Scheme 3: Proposed mechanism.
Copper-catalyzed enantioselective conjugate addition of organometallic reagents to challenging Michael acceptors
- Delphine Pichon,
- Jennifer Morvan,
- Christophe Crévisy and
- Marc Mauduit
Beilstein J. Org. Chem. 2020, 16, 212–232, doi:10.3762/bjoc.16.24
- enantioselective catalysis was reported by Evans and co-workers in 2005 [34]. The selected asymmetric transformation was the Friedel–Crafts 1,4-addition involving indole derivatives as nucleophiles, catalyzed by a scandium(III) triflate complex with chiral bis(oxazolinyl)pyridine ligands. As highlighted by Evans
Graphical Abstract
Scheme 1: Competitive side reactions in the Cu ECA of organometallic reagents to α,β-unsaturated aldehydes.
Scheme 2: Cu-catalyzed ECA of α,β-unsaturated aldehydes with phosphoramidite- (a) and phosphine-based ligands...
Scheme 3: One-pot Cu-catalyzed ECA/organocatalyzed α-substitution of enals.
Scheme 4: Combination of copper and amino catalysis for enantioselective β-functionalizations of enals.
Scheme 5: Optimized conditions for the Cu ECAs of R2Zn, RMgBr, and AlMe3 with α,β-unsaturated aldehydes.
Scheme 6: CuECA of Grignard reagents to α,β-unsaturated thioesters and their application in the asymmetric to...
Scheme 7: Improved Cu ECA of Grignard reagents to α,β-unsaturated thioesters, and their application in the as...
Scheme 8: Catalytic enantioselective synthesis of vicinal dialkyl arrays via Cu ECA of Grignard reagents to γ...
Scheme 9: 1,6-Cu ECA of MeMgBr to α,β,γ,δ-bisunsaturated thioesters: an iterative approach to deoxypropionate...
Scheme 10: Tandem Cu ECA/intramolecular enolate trapping involving 4-chloro-α,β-unsaturated thioester 22.
Scheme 11: Cu ECA of Grignard reagents to 3-boronyl α,β-unsaturated thioesters.
Scheme 12: Cu ECA of alkylzirconium reagents to α,β-unsaturated thioesters.
Scheme 13: Conversion of acylimidazoles into aldehydes, ketones, acids, esters, amides, and amines.
Scheme 14: Cu ECA of dimethyl malonate to α,β-unsaturated acylimidazole 31 with triazacyclophane-based ligand ...
Scheme 15: Cu/L13-catalyzed ECA of alkylboranes to α,β-unsaturated acylimidazoles.
Scheme 16: Cu/hydroxyalkyl-NHC-catalyzed ECA of dimethylzinc to α,β-unsaturated acylimidazoles.
Scheme 17: Stereocontrolled synthesis of 3,5,7-all-syn and anti,anti-stereotriads via iterative Cu ECAs.
Scheme 18: Stereocontrolled synthesis of anti,syn- and anti,anti-3,5,7-(Me,OR,Me) units via iterative Cu ECA/B...
Scheme 19: Cu-catalyzed ECA of dialkylzinc reagents to α,β-unsaturated N-acyloxazolidinones.
Scheme 20: Cu/phosphoramidite L16-catalyzed ECA of dialkylzincs to α,β-unsaturated N-acyl-2-pyrrolidinones.
Scheme 21: Cu/(R,S)-Josiphos (L9)-catalyzed ECA of Grignard reagents to α,β-unsaturated amides.
Scheme 22: Cu/Josiphos (L9)-catalyzed ECA of Grignard reagents to polyunsaturated amides.
Scheme 23: Cu-catalyzed ECA of trimethylaluminium to N-acylpyrrole derivatives.
New α- and β-cyclodextrin derivatives with cinchona alkaloids used in asymmetric organocatalytic reactions
- Iveta Chena Tichá,
- Simona Hybelbauerová and
- Jindřich Jindřich
Beilstein J. Org. Chem. 2019, 15, 830–839, doi:10.3762/bjoc.15.80
- , Czech Republic 10.3762/bjoc.15.80 Abstract The preparation of new organocatalysts for asymmetric syntheses has become a key stage of enantioselective catalysis. In particular, the development of new cyclodextrin (CD)-based organocatalysts allowed to perform enantioselective reactions in water and to
Graphical Abstract
Figure 1: Schematic cone-shaped (a) and structure representations (b) of α-CD (six glucopyranoside units) and...
Figure 2: Common cinchona alkaloids (cinchonine, cinchonidine, quinine, quinidine).
Scheme 1: CuAAC click reaction of propargylated cinchona alkaloids 3a–d with 6I-azido-6I-deoxy-α-CD (1) and 6I...
Scheme 2: CuAAC click reaction of per-Me-N3-α-CD (6) or per-Me-N3-β-CD (7) and propargylated cinchona alkaloi...
Scheme 3: Synthesis of difunctionalized α-CD 11 with quinine moieties.
Figure 3: Representative 1H NMR spectrum of the non-methylated quinidine–α-CD derivative 4d.
Figure 4: Representative 13C NMR spectrum and parts of the HMBC spectrum of the non-methylated quinidine–α-CD...
Scheme 4: AAA reaction of MBH carbamate 12 catalyzed by the prepared CD derivatives 4a–d, 5a–d, 8a–d, 9a–d, 11...
Ruthenium-based olefin metathesis catalysts with monodentate unsymmetrical NHC ligands
- Veronica Paradiso,
- Chiara Costabile and
- Fabia Grisi
Beilstein J. Org. Chem. 2018, 14, 3122–3149, doi:10.3762/bjoc.14.292
- to 19b, resulting in 90% conversion within 3 hours [17]. No relevant differences in the catalyst reactivity were observed for the CM of 13 and 14 (Scheme 4). As a novel application of N-aryl, N’-aryl unsymmetrical ruthenium complexes in enantioselective catalysis, Grela and Schmidt very recently
Graphical Abstract
Figure 1: Second-generation Grubbs (GII), Hoveyda (HGII), Grela (Gre-II), Blechert (Ble-II) and indenylidene-...
Figure 2: Grubbs (1a) and Hoveyda-type (1b) complexes with N-phenyl, N’-mesityl NHCs.
Figure 3: C–H insertion product 2.
Figure 4: Grubbs (3a–6a) and Hoveyda-type (3b–6b) complexes with N-fluorophenyl, N’-aryl NHCs.
Scheme 1: RCM of diethyl diallylmalonate (7).
Scheme 2: RCM of diethyl allylmethallylmalonate (9).
Scheme 3: RCM of diethyl dimethallylmalonate (11).
Scheme 4: CM of allylbenzene (13) with cis-1,4-diacetoxy-2-butene (14).
Scheme 5: ROMP of 1,5-cyclooctadiene (16).
Figure 5: Grubbs (18a–21a) and Hoveyda-type (18b–21b) catalysts bearing uNHCs with a hexafluoroisopropylalkox...
Figure 6: A Grubbs-type complex with an N-adamantyl, N’-mesityl NHC 22 and the Hoveyda-type complex with a ch...
Figure 7: Grubbs (24a and 25a) and Hoveyda-type (24b and 25b) complexes with N-alkyl, N’-mesityl NHCs.
Figure 8: Grubbs-type complexes 31–34 with N-alkyl, N’-mesityl NHCs.
Figure 9: Grubbs-type complex 35 with an N-cyclohexyl, N’-2,6-diisopropylphenyl NHC.
Figure 10: Hoveyda-type complexes with an N-alkyl, N’-mesityl (36, 37) and an N-alkyl, N’-2,6-diisopropylpheny...
Figure 11: Indenylidene-type complexes 41–43 with N-alkyl, N’-mesityl NHCs.
Figure 12: Grubbs-type complex 44 and its monopyridine derivative 45 containing a chiral uNHC.
Scheme 6: Alternating copolymerization of 46 with 47 and 48.
Figure 13: Pyridine-containing complexes 49–52 and Grubbs-type complex 53.
Figure 14: Hoveyda-type complexes 54–58 in the alternating ROMP of NBE (46) and COE (47).
Figure 15: Catalysts 59 and 60 in the tandem RO–RCM of 47.
Figure 16: Hoveyda-type complexes 61–69 with N-alkyl, N’-aryl NHCs.
Scheme 7: Ethenolysis of methyl oleate (70).
Scheme 8: AROCM of cis-5-norbornene-endo-2,3-dicarboxylic anhydride (75) with styrene.
Figure 17: Hoveyda-type catalysts 79–82 with N-tert-butyl, N’-aryl NHCs.
Scheme 9: Latent ROMP of 83 with catalyst 82.
Figure 18: Indenylidene and Hoveyda-type complexes 85–92 with N-cycloalkyl, N’-mesityl NHCs.
Scheme 10: RCM of N,N-dimethallyl-N-tosylamide (93) with catalyst 85.
Scheme 11: Self metathesis of 13 with catalyst 85.
Figure 19: Grubbs-type complexes 98–104 with N-alkyl, N’-mesityl NHCs.
Figure 20: Grubbs-type complexes 105–115 with N-alkyl, N’-mesityl ligands.
Figure 21: Complexes 116 and 117 bearing a carbohydrate-based NHC.
Figure 22: Complexes 118 and 119 bearing a hemilabile amino-tethered NHC.
Figure 23: Indenylidene-type complexes 120–126 with N-benzyl, N’-mesityl NHCs.
Scheme 12: Diastereoselective ring-rearrangement metathesis (dRRM) of cyclopentene 131.
Figure 24: Indenylidene-type complexes 134 and 135 with N-nitrobenzyl, N’-mesityl NHCs.
Figure 25: Hoveyda-type complexes 136–138 with N-benzyl, N’-mesityl NHCs.
Figure 26: Hoveyda-type complexes 139–142 with N-benzyl, N’-Dipp NHC.
Figure 27: Indenylidene (143–146) and Hoveyda-type (147) complexes with N-heteroarylmethyl, N’-mesityl NHCs.
Figure 28: Hoveyda-type complexes 148 and 149 with N-phenylpyrrole, N’-mesityl NHCs.
Figure 29: Grubbs-type complexes with N-trifluoromethyl benzimidazolidene NHCs 150–153, 155 and N-isopropyl be...
Scheme 13: Ethenolysis of ethyl oleate 156.
Scheme 14: Ethenolysis of cis-cyclooctene (47).
Figure 30: Grubbs-type C1-symmetric (164) and C2-symmetric (165) catalysts with a backbone-substituted NHC.
Figure 31: Possible syn and anti rotational isomers of catalyst 164.
Scheme 15: ARCM of substrates 166, 168 and 170.
Figure 32: Hoveyda (172) and Grubbs-type (173,174) backbone-substituted C1-symmetric NHC complexes.
Scheme 16: ARCM of 175,177 and 179 with catalyst 174.
Figure 33: Grubbs-type C1-symmetric NHC catalysts bearing N-propyl (181, 182) or N-benzyl (183, 184) groups on...
Scheme 17: ARCM of 185 and 187 promoted by 184 to form the encumbered alkenes 186 and 188.
Figure 34: N-Alkyl, N’-isopropylphenyl NHC ruthenium complexes with syn (189, 191) and anti (190, 192) phenyl ...
Figure 35: Hoveyda-type complexes 193–198 bearing N-alkyl, N’-aryl backbone-substituted NHC ligands.
Scheme 18: ARCM of 166 and 199 promoted by 192b.
Figure 36: Enantiopure catalysts 201a and 201b with syn phenyl units on the NHC backbone.
Figure 37: Backbone-monosubstituted catalysts 202–204.
Figure 38: Grubbs (205a) and Hoveyda-type (205b) backbone-monosubstituted catalysts.
Scheme 19: AROCM of 206 with allyltrimethylsilane promoted by catalyst 205a.
D-Fructose-based spiro-fused PHOX ligands: synthesis and application in enantioselective allylic alkylation
- Michael R. Imrich,
- Jochen Kraft,
- Cäcilia Maichle-Mössmer and
- Thomas Ziegler
Beilstein J. Org. Chem. 2018, 14, 2082–2089, doi:10.3762/bjoc.14.182
- enantioselectivity [1][2]. Probably the most effective approach in stereoselective synthesis is enantioselective catalysis, because cheap prochiral starting materials can be converted into chiral enantiopure products and no undesirable side products are formed [3][4]. Therefore, the development of new ligands is
- starting from D-fructose. Two of these ligands were applied in enantioselective catalysis. Results and Discussion Starting from D-fructose, 1,2-isopropylidene-protected pyranosides with different protective groups (PG) at C-3, C-4 and C-5 can be prepared in two to four steps (Scheme 1). First, D-fructose
Graphical Abstract
Figure 1: General structure of PHOX ligands 1 and structures of annulated glucosamine-based PHOX and PyOx lig...
Scheme 1: Preparation of 1,2-isopropylidene-protected D-fructose derivatives with different substitution patt...
Scheme 2: Activation of 7 to oxocarbenium ion 9 in the Ritter reaction.
Scheme 3: Zemplén deacetylation of 10i.
Figure 2: Molecular structure of 10j. Ellipsoids are given at the 50% probability level. Grey = carbon, red =...
Scheme 4: Benzylation of 10j to give 10b.
Scheme 5: Plausible mechanism of the Ritter reaction. For better clarity C-2 is not shown in conformers 9a an...
Scheme 6: Neighboring group participation of ester protective groups. For better clarity C-2 is not shown in ...
Scheme 7: Pd catalyzed Tsuji–Trost reation. BSA: N,O-bis(trimethylsilyl)acetamide, DMM: dimethyl malonate.
Strategies in asymmetric catalysis
- Tehshik P. Yoon
Beilstein J. Org. Chem. 2017, 13, 63–64, doi:10.3762/bjoc.13.8
- reactions. Those of us with research interests in stereoselective synthesis lauded this award because it celebrated the creative insights of these pioneers in asymmetric catalysis and because it marked a general recognition that enantioselective catalysis has had a significant practical impact on the
Stereodynamic tetrahydrobiisoindole “NU-BIPHEP(O)”s: functionalization, rotational barriers and non-covalent interactions
- Golo Storch,
- Sebastian Pallmann,
- Frank Rominger and
- Oliver Trapp
Beilstein J. Org. Chem. 2016, 12, 1453–1458, doi:10.3762/bjoc.12.141
- Golo Storch Sebastian Pallmann Frank Rominger Oliver Trapp Organisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany 10.3762/bjoc.12.141 Abstract Stereodynamic ligands offer intriguing possibilities in enantioselective catalysis. “NU
- preparation of tailor-made functionalized stereodynamic ligands possible and give an outline for possible applications in enantioselective catalysis. Keywords: atropisomer; enantioselective DHPLC; ligand design; non-covalent interactions; Okamoto phases; phosphine ligand; stereodynamic ligands; Introduction
- ’-biphenyl) ligands have a significantly lower barrier of rotation around the central C–C bond regarding the conversion of the enantiomers into one another. This enables fast enantiomerization at room temperature. This, however, does not conflict with their usage in enantioselective catalysis. Noyori and
Graphical Abstract
Figure 1: Synthetic overview of “NU-BIPHEP(O)s”. A) Rhodium catalyzed double [2 + 2 + 2] cycloaddition. B) Ac...
Figure 2: Investigation of 3,5-dichlorobenzoyl modified tetrahydrobiisoindole “NU-BIPHEP(O)” 3. A) Three sign...
Figure 3: Investigation of “NU-BIPHEP(O)” 1b. A) Solid-state structure determined by X-ray crystallography. H...
Figure 4: Enantioselective DHPLC investigation of tetrahydrobiisoindole “NU-BIPHEP(O)” 3. A) Elution profiles...
Selective bromochlorination of a homoallylic alcohol for the total synthesis of (−)-anverene
- Frederick J. Seidl and
- Noah Z. Burns
Beilstein J. Org. Chem. 2016, 12, 1361–1365, doi:10.3762/bjoc.12.129
- homoallylic alcohol. Critical factors for optimization of this reaction are highlighted. The utility of the product bromochloride is demonstrated by the first total synthesis of an antibacterial polyhalogenated monoterpene, (−)-anverene. Keywords: enantioselective catalysis; halogenation; natural products
Graphical Abstract
Scheme 1: Selective bromochlorination and possible disconnections for anverene (1).
Scheme 2: Selective total synthesis of (−)-anverene. Reagents and conditions: a) NBS (1.2 equiv), ClTi(OiPr)3...
Copper-catalyzed asymmetric conjugate addition of organometallic reagents to extended Michael acceptors
- Thibault E. Schmid,
- Sammy Drissi-Amraoui,
- Christophe Crévisy,
- Olivier Baslé and
- Marc Mauduit
Beilstein J. Org. Chem. 2015, 11, 2418–2434, doi:10.3762/bjoc.11.263
- control of the regio- and enantioselectivity of the addition. The aim of this review is to report recent breakthroughs achieved in this challenging field. Keywords: conjugate additions; electron-deficient alkenes; enantioselective catalysis; extended Michael acceptors; organometallic nucleophiles
Graphical Abstract
Figure 1: Possible reaction pathways in conjugate additions of nucleophiles on extended Michael acceptors.
Figure 2: Early reports of conjugate addition of copper-based reagents to extended Michael acceptors.
Figure 3: First applications of copper catalyzed 1,6-ACA in total synthesis.
Scheme 1: First example of enantioselective copper-catalyzed ACA on an extended Michael acceptor.
Scheme 2: Meldrum’s acid derivatives as substrates in enantioselective ACA.
Scheme 3: Reactivity of a cyclic dienone in Cu-catalyzed ACA of diethylzinc.
Scheme 4: Efficiency of DiPPAM ligand in 1,6-ACA of dialkylzinc to cyclic dienones.
Scheme 5: Sequential 1,6/1,4-ACA reactions involving linear aryldienones.
Scheme 6: Unsymmetrical hydroxyalkyl NHC ligands in 1,6-ACA of cyclic dienones.
Scheme 7: Performance of atropoisomeric diphosphines in 1,6-ACA of Et2Zn on cyclic dienones.
Scheme 8: Selective 1,6-ACA of Grignard reagents to acyclic dienoates, application in total synthesis.
Scheme 9: Reactivity of polyenic linear thioesters towards sequential 1,6-ACA/reconjugation/1,4-ACA and produ...
Scheme 10: 1,6-Conjugate addition of trialkylaluminium with regards to cyclic dienones.
Scheme 11: Copper-catalyzed conjugate addition of trimethylaluminium onto nitro dienoates.
Scheme 12: Copper-catalyzed selective 1,4-ACA in total synthesis of erogorgiaene.
Scheme 13: 1,4-selective addition of diethylzinc onto a cyclic enynone catalyzed by a chiral NHC-based system.
Scheme 14: Cu-NHC-catalyzed 1,6-ACA of dimethylzinc onto an α,β,γ,δ-unsaturated acyl-N-methylimidazole.
Scheme 15: 1,4-Selectivity in conjugate addition on extended systems with the concomitant use of a chelating c...
Scheme 16: Cu-NHC catalyzed 1,4-ACA as the key step in the total synthesis of ent-riccardiphenol B.
Scheme 17: Cu-NHC-catalyzed 1,4-selective ACA reactions with enynones.
Scheme 18: Linear dienones as substrates in 1,4-asymmetric conjugate addition reactions of Grignard reagents c...
Scheme 19: 1,4-ACA of trimethylaluminium to a cyclic enynone catalyzed by a copper-NHC system.
Scheme 20: Generation of a sterically encumbered chiral cyclohexanone from a polyunsaturated cyclic Michael ac...
Scheme 21: Selective conversion of β,γ-unsaturated α-ketoesters in copper-catalyzed asymmetric conjugate addit...
Scheme 22: Addition of trialkylaluminium compounds to nitroenynes catalyzed by L9/CuTC.
Scheme 23: Addition of trialkylaluminium compounds to nitrodienes catalyzed by L9/CuTC.
Scheme 24: Copper catalyzed 1,8- and 1,10-ACA reactions.
A new charge-tagged proline-based organocatalyst for mechanistic studies using electrospray mass spectrometry
- J. Alexander Willms,
- Rita Beel,
- Martin L. Schmidt,
- Christian Mundt and
- Marianne Engeser
Beilstein J. Org. Chem. 2014, 10, 2027–2037, doi:10.3762/bjoc.10.211
- -tagged substrates have been used to easily identify (“fish for”) efficient catalysts [6][9]. Since the year 2000, enantioselective catalysis based on small organic metal-free molecules has become an enormously growing research topic [24][25][26][27][28][29][30]. A large variety of organocatalyzed
Graphical Abstract
Figure 1: The new charge-tagged proline-derived catalyst 1.
Scheme 1: Inverse aldol reaction with aldehyde donors according to Jørgensen [54]. We studied the reaction for R ...
Scheme 2: Synthesis of 4-(pyridin-4-yl)phenol (5).
Scheme 3: Synthesis of the charge-tagged proline catalyst 1.
Figure 2: Molecular structure of 7 in the solid state.
Scheme 4: Proposed catalytic cycle [36-38] for the aldol reaction with aldehyde donors [54]; CT = charge tag, a: R = Ph, ...
Figure 3: Experimental setup for continuous-flow ESIMS experiments using two mixing tee microreactors directl...
Figure 4: ESI mass spectra of acetonitrile solutions of diethyl ketomalonate and butyraldehyde (a) with unmod...
Figure 5: ESI(+) CID MS/MS spectra of mass-selected intermediates a) [IIb]+, b) the butyl ester derivative [I...
Figure 6: Normalized relative intensities in ESI spectra recorded for the inverse aldol reaction of butyralde...
Primary-tertiary diamine-catalyzed Michael addition of ketones to isatylidenemalononitrile derivatives
- Akshay Kumar and
- Swapandeep Singh Chimni
Beilstein J. Org. Chem. 2014, 10, 929–935, doi:10.3762/bjoc.10.91
- % yield, 82:18 dr and 98% ee (Scheme 4). Conclusion In conclusion, we successfully demonstrated the use of the very simple primary-tertiary diamine catalyst 1a in combination with D-CSA as an additive for the enantioselective catalysis of a Michael addition of acetone to isatylidenemalononitriles. A three
Graphical Abstract
Figure 1: Oxindole based Michael acceptors.
Figure 2: Primary-tertiary diamine organocatalysts.
Scheme 1: Diamine catalyzed Michael addition of acetone to isatylidenemalononitrile.
Scheme 2: Substrate scope of the addition of 2 with 3 catalyzed by 1a D-CSA.
Scheme 3: One-pot, three-component Knoevenagel condensation–Michael addition.
Scheme 4: Cascade reduction–cyclization for the synthesis of spirooxindole.
New hydrogen-bonding organocatalysts: Chiral cyclophosphazanes and phosphorus amides as catalysts for asymmetric Michael additions
- Helge Klare,
- Jörg M. Neudörfl and
- Bernd Goldfuss
Beilstein J. Org. Chem. 2014, 10, 224–236, doi:10.3762/bjoc.10.18
- to 2-hydroxy-1,4-naphthoquinone With these novel catalysts in hands we tested their efficiency in enantioselective catalysis. The reaction of 2-hydroxy-1,4-naphthoquinone (17) with β-nitrostyrene (18) is well-suited for comparison because it has already been studied while employing thiourea
Graphical Abstract
Figure 1: Thiourea, squaramide, P-triamide and cyclodiphosphazane with computed distances between H-atoms.
Figure 2: Urea, squaramide, P-triamide and cyclodiphosphazane coordinated to nitrobenzene, with the computed ...
Scheme 1: Chiral PV-amide catalysts based on BINOL and chinchona backbones.
Scheme 2: Exclusive formation of the mono- and trisubstituted product from thiophosphoryl chloride and anilin...
Figure 3: X-ray structure of 6-dimer. The hydrogen atoms are omitted for clarity, except at all nitrogens.
Figure 4: X-ray structure of 7a-dimer. The hydrogen atoms are omitted for clarity, except at all nitrogens.
Scheme 3: Synthesis of chiral cyclodiphosphazane catalysts 14a/b, 15 and 16.
Figure 5: X-ray structure of 14a. The hydrogen atoms are omitted for clarity, except at nitrogen.
Figure 6: 31P{1H} NMR spectrum in CDCl3 at rt showing C2 symmetry of 14a at rt.
Figure 7: X-ray structure of 15. The hydrogen atoms are omitted for clarity, except at nitrogen.
Figure 8: X-ray structure of 16. The hydrogen atoms are omitted for clarity, except at nitrogen.
Figure 9: Enantiodetermining transition states TS-14a/TS-14b arising from the addition of 2-hydroxynapthoquin...
