Search for "nitrile" in Full Text gives 253 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Beilstein J. Org. Chem. 2015, 11, 1667–1699, doi:10.3762/bjoc.11.183
Graphical Abstract
Figure 1: Fragments produced by the FAB–MS of dehydrokuanoniamine B (20) [42].
Figure 2: Fragments produced by the EIMS of sagitol (26) [55].
Figure 3: Fragments produced by the EIMS of styelsamine B (4) [45].
Figure 4: Fragments produced by the EIMS of styelsamine D (6) [45].
Figure 5: Fragments produced by the EIMS of subarine (37) [40].
Scheme 1: Synthesis of styelsamine B (4) and cystodytin J (1) [58].
Scheme 2: Synthesis of sebastianine A (38) and its regioisomer 39 [59].
Scheme 3: Synthesis route A of neoamphimedine (12) [61].
Scheme 4: Synthesis route B of neoamphimedine (12) [62].
Scheme 5: Synthesis of arnoamines A (40) and B (41) [63].
Scheme 6: Synthesis of ascididemin (42) [65].
Scheme 7: Synthesis of subarine (37) [66,67].
Scheme 8: Synthesis of demethyldeoxyamphimedine (9) [68].
Scheme 9: Synthesis of pyridoacridine analogues related to ascididemin (42) [70].
Scheme 10: Synthesis of analogues of meridine (56) [71].
Scheme 11: Synthesis of bulky pyridoacridine as eilatin (58) [72].
Scheme 12: Synthesis of AK37 (59), analogue of kuanoniamine A (60) [73].
Figure 6: Biosynthesis pathway I [74].
Figure 7: Reaction illustrating catechol and kynuramine as possible biosynthetic precursors [75].
Figure 8: Biosynthesis pathway B deduced from the feeding experiment A using labelled precursors [76].
Figure 9: Proposed biosynthesis pathway [47].
Figure 10: 4H-Pyrido[2,3,4-kl]acridin-4-one as a cytotoxic pharmacophore.
Figure 11: 7H-Pyrido[2,3,4-kl]acridine as a cytotoxic pharmacophore.
Figure 12: 9H-Quinolino[4,3,2-de][1,10]phenanthrolin-9-one as a cytotoxic pharmacophore.
Figure 13: 8H-Benzo[b]pyrido[4,3,2-de][1,7]phenanthrolin-8-one as a cytotoxic pharmacophore.
Figure 14: Pyrido[4,3,2-mn]pyrrolo[3,2,1-de]acridine as a cytotoxic pharmacophore.
Figure 15: 9H-Pyrido[4,3,2-mn]thiazolo[4,5-b]acridin-9-one and 8H-pyrido[4,3,2-mn]thiazolo[4,5-b]acridine: cyt...
Figure 16: 9H-quinolino[4,3,2-de][1,10]phenanthrolin-9-one as an anti-mycobacterial pharmacophore.
Figure 17: 9H-Quinolino[4,3,2-de][1,10]phenanthrolin-9-one as an antibacterial pharmacophore.
Figure 18: Saturated and less saturated pyridine moieties as aspartyl inhibitor cores.
Figure 19: Iminobenzoquinone and acridone cores as intercalating and TOPO inhibitor motifs found in pyridoacri...
Beilstein J. Org. Chem. 2015, 11, 1241–1245, doi:10.3762/bjoc.11.138
Graphical Abstract
Scheme 1: A strategy for developing functionalized nitrile oxides.
Figure 1: Versatile functionalized nitrile oxides.
Beilstein J. Org. Chem. 2015, 11, 1194–1219, doi:10.3762/bjoc.11.134
Graphical Abstract
Figure 1: Pharmaceutical structures targeted in early flow syntheses.
Scheme 1: Flow synthesis of 6-hydroxybuspirone (9). Inserted photograph reprinted with permission from [45]. Copy...
Figure 2: Configuration of a baffled reactor tube (left) and its schematic working principle (right).
Scheme 2: McQuade’s flow synthesis of ibuprofen (16).
Scheme 3: Jamison’s flow synthesis of ibuprofen sodium salt (17).
Scheme 4: Flow synthesis of imatinib (23).
Scheme 5: Flow synthesis of the potent 5HT1B antagonist 28.
Scheme 6: Flow synthesis of a selective δ-opioid receptor agonist 33.
Scheme 7: Flow synthesis of a casein kinase I inhibitor library (38).
Scheme 8: Flow synthesis of fluoxetine (46).
Scheme 9: Flow synthesis of artemisinin (55).
Scheme 10: Telescoped flow synthesis of artemisinin (55) and derivatives (62–64).
Scheme 11: Flow approach towards AZD6906 (65).
Scheme 12: Pilot scale flow synthesis of key intermediate 73.
Scheme 13: Semi-flow synthesis of vildagliptine (77).
Scheme 14: Pilot scale asymmetric flow hydrogenation towards 83. Inserted photograph reprinted with permission...
Figure 3: Schematic representation of the ‘tube-in-tube’ reactor.
Scheme 15: Flow synthesis of fanetizole (87) via tube-in-tube system.
Scheme 16: Flow synthesis of diphenhydramine.HCl (92).
Scheme 17: Flow synthesis of rufinamide (95).
Scheme 18: Large scale flow synthesis of rufinamide precursor 102.
Scheme 19: First stage in the flow synthesis of meclinertant (103).
Scheme 20: Completion of the flow synthesis of meclinertant (103).
Scheme 21: Flow synthesis of olanzapine (121) utilising inductive heating techniques.
Scheme 22: Flow synthesis of amitriptyline·HCl (127).
Scheme 23: Flow synthesis of E/Z-tamoxifen (132) using peristaltic pumping modules.
Figure 4: Container sized portable mini factory (photograph credit: INVITE GmbH, Leverkusen Germany).
Scheme 24: Flow synthesis of imidazo[1,2-a]pyridines 136 linked to frontal affinity chromatography (FAC).
Figure 5: Structures of zolpidem (142) and alpidem (143).
Scheme 25: Synthesis and screening loops in the discovery of new Abl kinase inhibitors.
Figure 6: Schotten–Baumann approach towards LY573636.Na (147).
Scheme 26: Pilot scale flow synthesis of LY2886721 (146).
Scheme 27: Continuous flow manufacture of alikiren hemifumarate 152.
Beilstein J. Org. Chem. 2015, 11, 875–883, doi:10.3762/bjoc.11.98
Graphical Abstract
Figure 1: Selected examples of biologically active thiazole containing molecules [12-20].
Scheme 1: Illustration of substrates that form thiophenes under Gewald-type conditions.
Figure 2: Substrates which did not react under the optimised conditions.
Scheme 2: Proposed mechanisms for the formation of thiazoles.
Beilstein J. Org. Chem. 2015, 11, 647–658, doi:10.3762/bjoc.11.73
Graphical Abstract
Scheme 1: Mesomeric forms of 1,3-dithiole rings substituted with EWG.
Scheme 2: Investigated TTF derivatives bearing EWG.
Scheme 3: Synthetic procedures to the CF3-substituted 4bc, 1c and 2ac molecules.
Scheme 4: Synthetic procedure to 3bc.
Figure 1: Correlation between the first oxidation potential E1/2 and the sum of the Hammet σmeta parameters. ...
Figure 2: Calculated frontier orbitals of geometry-optimized [B3LYP/6-31G(d)] model compounds TTF, TTF-CF3, T...
Figure 3: View of the 2ac molecule. Thermal ellipsoids are shown at the 50% probability level.
Figure 4: View of the 2bc molecule. Thermal ellipsoids are shown at the 50% probability level.
Figure 5: View of the two crystallographically independent 4bc molecules. Thermal ellipsoids are shown at the...
Figure 6: View of the 3bc molecule. Note the disordered CF3 groups as well as the CO2Me group orthogonal to t...
Figure 7: A view of the alternated stacks along the b axis in (1c)2(TCNQ).
Figure 8: Detail of the overlap between donor and acceptor molecules in (1c)2(TCNQ).
Figure 9: Projection view along the a axis of the unit cell of (1c+•)(FeCl4−).
Beilstein J. Org. Chem. 2015, 11, 628–637, doi:10.3762/bjoc.11.71
Graphical Abstract
Scheme 1: Molecular diagrams of α-tbtdt (1) and α-mtdt (2), and related TTF-type donors.
Scheme 2: Synthetic route for compounds 1 and 2.
Figure 1: Cyclic voltammogram of α-tbtdt (1) and α-mtdt (2) (10−3 M) in dichloromethane versus Ag/AgNO3, with ...
Figure 2: ORTEP view and atomic numbering scheme of I with thermal ellipsoids at 50% probability level.
Figure 3: Molecular herringbone bi-chains in the crystal structure of I: a) view along the molecular planes a...
Figure 4: Crystal structure of I a) view along the b axis, b) Partial view of one layer of bi-chains in the a...
Figure 5: ORTEP views and atomic numbering scheme of α-tbtdt (1) with thermal ellipsoids at 50% probability l...
Figure 6: Crystal structure of 1 a) view along the b axis; b) Partial view of one chain in the b,c plane (top...
Figure 7: ORTEP views and atomic numbering scheme of a) (α-mtdt)+ and b) [Au(mnt)2 ]− in compound 3, with the...
Figure 8: Crystal structure of 3 a) viewed along the b axis and b) partial view showing the alternated A–D–A–...
Figure 9: Detail of the crystal structure of 3 showing the short contacts between stacks.
Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13
Graphical Abstract
Scheme 1: Cross-dehydrogenative coupling.
Scheme 2: Cross-dehydrogenative C–O coupling.
Scheme 3: Regioselective ortho-acetoxylation of meta-substituted arylpyridines and N-arylamides.
Scheme 4: ortho-Acyloxylation and alkoxylation of arenes directed by pyrimidine, benzoxazole, benzimidazole a...
Scheme 5: Cu(OAc)2/AgOTf/O2 oxidative system in the ortho-alkoxylation of arenes.
Scheme 6: Pd(OAc)2/persulfate oxidative system in the ortho-alkoxylation and acetoxylation of arenes with nit...
Scheme 7: ortho-Acetoxylation and methoxylation of O-methyl aryl oximes, N-phenylpyrrolidin-2-one, and (3-ben...
Scheme 8: Ruthenium-catalyzed ortho-acyloxylation of acetanilides.
Scheme 9: Acetoxylation and alkoxylation of arenes with amide directing group using Pd(OAc)2/PhI(OAc)2 oxidat...
Scheme 10: Alkoxylation of azoarenes, 2-aryloxypyridines, picolinamides, and N-(1-methyl-1-(pyridin-2-yl)ethyl...
Scheme 11: Acetoxylation of compounds containing picolinamide and quinoline-8-amine moieties using the Pd(OAc)2...
Scheme 12: (CuOH)2CO3 catalyzed oxidative ortho-etherification using air as oxidant.
Scheme 13: Copper-catalyzed aerobic alkoxylation and aryloxylation of arenes containing pyridine-N-oxide moiet...
Scheme 14: Cobalt-catalyzed aerobic alkoxylation of arenes and alkenes containing pyridine N-oxide moiety.
Scheme 15: Non-symmetric double-fold C–H ortho-acyloxylation.
Scheme 16: N-nitroso directed ortho-alkoxylation of arenes.
Scheme 17: Selective alkoxylation and acetoxylation of alkyl groups.
Scheme 18: Acetoxylation of 2-alkylpyridines and related compounds.
Scheme 19: Acyloxylation and alkoxylation of alkyl fragments of substrates containing amide or sulfoximine dir...
Scheme 20: Palladium-catalyzed double sp3 C–H alkoxylation of N-(quinolin-8-yl)amides for the synthesis of sym...
Scheme 21: Copper-catalyzed acyloxylation of methyl groups of N-(quinolin-8-yl)amides.
Scheme 22: One-pot acylation and sp3 C–H acetoxylation of oximes.
Scheme 23: Possible mechanism of oxidative esterification catalyzed by N-heterocyclic nucleophilic carbene.
Scheme 24: Oxidative esterification employing stoichiometric amounts of aldehydes and alcohols.
Scheme 25: Selective oxidative coupling of aldehydes with alcohols in the presence of amines.
Scheme 26: Iodine mediated oxidative esterification.
Scheme 27: Oxidative C–O coupling of benzyl alcohols with methylarenes under the action of Bu4NI/t-BuOOH syste...
Scheme 28: Oxidative coupling of methyl- and ethylarenes with aromatic aldehydes under the action of Bu4NI/t-B...
Scheme 29: Cross-dehydrogenative C–O coupling of aldehydes with t-BuOOH in the presence of Bu4NI.
Scheme 30: Bu4NI-catalyzed α-acyloxylation reaction of ethers and ketones with aldehydes and t-BuOOH.
Scheme 31: Oxidative coupling of aldehydes with N-hydroxyimides and hexafluoroisopropanol.
Scheme 32: Oxidative coupling of alcohols with N-hydroxyimides.
Scheme 33: Oxidative coupling of aldehydes and primary alcohols with N-hydroxyimides using (diacetoxyiodo)benz...
Scheme 34: Proposed mechanism of the oxidative coupling of aldehydes and N-hydroxysuccinimide under action of ...
Scheme 35: Oxidative coupling of aldehydes with pivalic acid (172).
Scheme 36: Oxidative C–O coupling of aldehydes with alkylarenes using the Cu(OAc)2/t-BuOOH system.
Scheme 37: Copper-catalyzed acyloxylation of C(sp3)-H bond adjacent to oxygen in ethers using benzyl alcohols.
Scheme 38: Oxidative C–O coupling of aromatic aldehydes with cycloalkanes.
Scheme 39: Ruthenium catalyzed cross-dehydrogenative coupling of primary and secondary alcohols.
Scheme 40: Cross-dehydrogenative C–O coupling reactions of β-dicarbonyl compounds with sulfonic acids, acetic ...
Scheme 41: Acyloxylation of ketones, aldehydes and β-dicarbonyl compounds using carboxylic acids and Bu4NI/t-B...
Scheme 42: Acyloxylation of ketones using Bu4NI/t-BuOOH system.
Scheme 43: Cross-dehydrogenative C–O coupling of β-dicarbonyl compounds and their heteroanalogues with N-hydro...
Scheme 44: Cross-dehydrogenative C–O coupling of β-dicarbonyl compounds and their heteroanalogues with t-BuOOH....
Scheme 45: Oxidative C–O coupling of 2,6-dialkylphenyl-β-keto esters and thioesters with tert-butyl hydroxycar...
Scheme 46: α’-Acyloxylation of α,β-unsaturated ketones using KMnO4.
Scheme 47: Possible mechanisms of the acetoxylation at the allylic position of alkenes by Pd(OAc)2.
Scheme 48: Products of the oxidation of terminal alkenes by Pd(II)/AcOH/oxidant system.
Scheme 49: Acyloxylation of terminal alkenes with carboxylic acids.
Scheme 50: Synthesis of linear E-allyl esters by cross-dehydrogenative coupling of terminal alkenes wih carbox...
Scheme 51: Pd(OAc)2-catalyzed acetoxylation of Z-vinyl(triethylsilanes).
Scheme 52: α’-Acetoxylation of α-acetoxyalkenes with copper(II) chloride in acetic acid.
Scheme 53: Oxidative acyloxylation at the allylic position of alkenes and at the benzylic position of alkylare...
Scheme 54: Copper-catalyzed alkoxylation of methylheterocyclic compounds using di-tert-butylperoxide as oxidan...
Scheme 55: Oxidative C–O coupling of methylarenes with β-dicarbonyl compounds or phenols.
Scheme 56: Copper-catalyzed esterification of methylbenzenes with cyclic ethers and cycloalkanes.
Scheme 57: Oxidative C–O coupling of carboxylic acids with toluene catalyzed by Pd(OAc)2.
Scheme 58: Oxidative acyloxylation at the allylic position of alkenes with carboxylic acids using the Bu4NI/t-...
Scheme 59: Cross-dehydrogenative C–O coupling of carboxylic acids with alkylarenes using the Bu4NI/t-BuOOH sys...
Scheme 60: Oxidative C–O cross-coupling of methylarenes with ethyl or isopropylarenes.
Scheme 61: Phosphorylation of benzyl C–H bonds using the Bu4NI/t-BuOOH oxidative system.
Scheme 62: Selective C–H acetoxylation of 2,3-disubstituted indoles.
Scheme 63: Acetoxylation of benzylic position of alkylarenes using DDQ as oxidant.
Scheme 64: C–H acyloxylation of diarylmethanes, 3-phenyl-2-propen-1-yl acetate and dimethoxyarene using DDQ.
Scheme 65: Cross-dehydrogenative C–O coupling of 1,3-diarylpropylenes and 1,3-diarylpropynes with alcohols.
Scheme 66: One-pot azidation and C–H acyloxylation of 3-chloro-1-arylpropynes.
Scheme 67: Cross-dehydrogenative C–O coupling of 1,3-diarylpropylenes, (E)-1-phenyl-2-isopropylethylene and is...
Scheme 68: Cross-dehydrogenative C–O coupling of alkylarenes and related compounds with N-hydroxyphthalimide.
Scheme 69: Acetoxylation at the benzylic position of alkylarenes mediated by N-hydroxyphthalimide.
Scheme 70: C–O coupling of methylarenes with aromatic carboxylic acids employing the NaBrO3/NaHSO3 system.
Scheme 71: tert-Butyl peroxidation of allyl, propargyl and benzyl ethers catalyzed by Fe(acac)3.
Scheme 72: Cross-dehydrogenative C–O coupling of ethers with carboxylic acids mediated by Bu4NI/t-BuOOH system....
Scheme 73: Oxidative acyloxylation of dimethylamides and dioxane with 2-aryl-2-oxoacetic acids accompanied by ...
Scheme 74: tert-Butyl peroxidation of N-benzylamides and N-allylbenzamide using the Bu4NI/t-BuOOH system.
Scheme 75: Cross-dehydrogenative C–O coupling of aromatic carboxylic acids with ethers using Fe(acac)3 as cata...
Scheme 76: Cross-dehydrogenative C–O coupling of cyclic ethers with 2-hydroxybenzaldehydes using iron carbonyl...
Scheme 77: Cross-dehydrogenative C–O coupling of ethers with β-dicarbonyl compounds and phenols using copper c...
Scheme 78: Cross-dehydrogenative C–O coupling of 2-hydroxybenzaldehyde with dioxane catalyzed by Cu2(BPDC)2(BP...
Scheme 79: Ruthenium chloride-catalyzed acyloxylation of β-lactams.
Scheme 80: Ruthenium-catalyzed tert-butyl peroxydation amides and acetoxylation of β-lactams.
Scheme 81: PhI(OAc)2-mediated α,β-diacetoxylation of tertiary amines.
Scheme 82: Electrochemical oxidative methoxylation of tertiary amines.
Scheme 83: Cross-dehydrogenative C–O coupling of ketene dithioacetals with carboxylic acids in the presence of...
Scheme 84: Cross-dehydrogenative C–O coupling of enamides with carboxylic acids using iodosobenzene as oxidant....
Scheme 85: Oxidative alkoxylation, acetoxylation, and tosyloxylation of acylanilides using PhI(O(O)CCF3)2 in t...
Scheme 86: Proposed mechanism of the oxidative C–O coupling of actetanilide with O-nucleophiles in the presenc...
Scheme 87: Three-component coupling of aldehydes, anilines and alcohols involving oxidative intermolecular C–O...
Scheme 88: Oxidative coupling of phenols with alcohols.
Scheme 89: 2-Acyloxylation of quinoline N-oxides with arylaldehydes in the presence of the CuOTf/t-BuOOH syste...
Scheme 90: Cross-dehydrogenative C–O coupling of azoles with primary alcohols.
Scheme 91: Oxidation of dipyrroles to dipyrrins and subsequent oxidative alkoxylation in the presence of Na3Co...
Scheme 92: Oxidative dehydrogenative carboxylation of alkanes and cycloalkanes to allylic esters.
Scheme 93: Pd-catalyzed acetoxylation of benzene.
Beilstein J. Org. Chem. 2015, 11, 85–91, doi:10.3762/bjoc.11.12
Graphical Abstract
Scheme 1: Anodic fluorination of sulfides having an electron-withdrawing group.
Scheme 2: Anodic fluorination of dithioacetals.
Figure 1: Dependency of fluorinated product selectivity on a series of fluoride salts (a) Et3N·nHF (n = 3–5) ...
Scheme 3: Plausible reaction mechanism for anodic fluorination of 1b, 1d, and 1f.
Scheme 4: Mechanism for suppression of the elimination of HF (deprotonation) and preferable desulfurization o...
Beilstein J. Org. Chem. 2014, 10, 3122–3126, doi:10.3762/bjoc.10.329
Graphical Abstract
Figure 1: Structures of aspergillides.
Scheme 1: Retrosynthetic analysis for (−)-aspergillide C.
Scheme 2: Synthesis of 11. Reaction conditions: (a) n-BuLi, THF/HMPA (5:1), −78 °C to rt, 12 h, 95%; (b) Li, t...
Figure 2: Key NOESY correlations observed in compound 11.
Scheme 3: Synthesis of 4 and formal total synthesis of (−)-aspergillide C (3). Reaction conditions: (a) [Cp*(...
Beilstein J. Org. Chem. 2014, 10, 3056–3072, doi:10.3762/bjoc.10.323
Graphical Abstract
Scheme 1: Application of anodic oxidation to the generation of new carbon-carbon bonds [11].
Scheme 2: The influence of the amino protecting group on the “kinetic” and “thermodynamic” anodic methoxylati...
Scheme 3: Example of the application of the cation pool method [17].
Scheme 4: A thiophenyl electroauxiliary allows for regioselective anodic oxidation [32].
Scheme 5: A diastereoselective cation carbohydroxylation reaction and postulated intermediate 18 [18].
Scheme 6: A radical addition and electron transfer reaction of N-acyliminium ions generated electrosynthetica...
Scheme 7: Catalytic indirect anodic fluorodesulfurization reaction [37].
Figure 1: Schematic of a cation flow system and also shown is the electrochemical microflow reactor reported ...
Figure 2: Example of a parallel laminar flow set-up. Figure redrawn from reference [38].
Figure 3: A catch and release cation pool method [42].
Scheme 8: Micromixing effects on yield 92% vs 36% and ratio of alkylation products [43].
Figure 4: Schematic illustration of the anodic substitution reaction system using acoustic emulsification. Fi...
Scheme 9: Electrooxidation to prepare a chiral oxidation mediator and application to the kinetic resolution o...
Scheme 10: Electrooxidation reactions on 4-membered ring systems [68].
Figure 5: Example of a chiral auxiliary Shono-oxidation intermediate [69].
Scheme 11: An electrochemical multicomponent reaction where a carbon felt anode and platinum cathode were util...
Scheme 12: Preparation of dienes using the Shono oxidation [23].
Scheme 13: Combination of an electroauxiliary mediated anodic oxidation and RCM to afford spirocyclic compound...
Scheme 14: Total synthesis of (+)-myrtine (66) using an electrochemical approach [78].
Scheme 15: Total synthesis of (−)-A58365A (70) and (±)-A58365B (71) [79].
Scheme 16: Anodic oxidation used in the preparation of the poison frog alkaloid 195C [80].
Scheme 17: Preparation of iminosugars using an electrochemical approach [81].
Scheme 18: The electrosynthetic preparation of α-L-fucosidase inhibitors [84,85].
Scheme 19: Enantioselective synthesis of the anaesthetic ropivacaine 85 [71].
Scheme 20: The preparation of synthetically challenging aza-nucleosides employing an electrochemical step [88].
Scheme 21: Synthesis of a bridged tricyclic diproline analogue 93 that induces α-helix conformation into linea...
Scheme 22: Synthesis of (i) a peptidomimetic and (ii) a functionalised peptide from silyl electroauxiliary pre...
Scheme 23: Examples of Phe7–Phe8 mimics prepared using an electrochemical approach [93].
Scheme 24: Preparation of arginine mimics employing an electrooxidation step [96].
Scheme 25: Preparation of chiral cyclic amino acids [20].
Scheme 26: Two-step preparation of Nazlinine 117 using Shono flow electrochemistry [101].
Beilstein J. Org. Chem. 2014, 10, 2729–2737, doi:10.3762/bjoc.10.288
Graphical Abstract
Scheme 1: Synthesis of nanodiamond derivatives carrying primary amino groups. a) Δ, b) 18-crown-6, KI, c) BH3...
Figure 1: FTIR-spectra of annealed nanodiamond 2 (a), nitrile 4 (b) and amine 5 (c). As can be seen from the ...
Figure 2: FTIR spectra (left) of compounds 2 (a), 9 (b), 10 (c) and 11 (d). The formation of the sulfone grou...
Figure 3: Modified Kaiser test. a) Left: control, right: positive result; b) left: control, control with prem...
Beilstein J. Org. Chem. 2014, 10, 2230–2234, doi:10.3762/bjoc.10.231
Graphical Abstract
Scheme 1: Functionalization of carbohydrates; reagents and conditions: (a) In, allyl bromide, EtOH/H2O, ultra...
Scheme 2: Deprotection sequence; reagents and conditions: (a): HCl/MeOH, rt, 16–24 h, then MeOH, CH2Cl2, O3, ...
Beilstein J. Org. Chem. 2014, 10, 1848–1877, doi:10.3762/bjoc.10.195
Graphical Abstract
Figure 1: Examples of phosphonamide reagents used in stereoselective synthesis.
Figure 2: Natural products and bioactive molecules synthesized using phosphonamide-based chemistry (atoms, bo...
Scheme 1: Olefination with cyclic phosphonamide anions, mechanistic rationale, and selected examples 27a–d [18].
Scheme 2: Asymmetric olefination with chiral phosphonamide anions and selected examples 31a–d [1,22].
Scheme 3: Synthesis of α-substituted phosphonic acids 33a–e by asymmetric alkylation of chiral phosphonamide ...
Scheme 4: Asymmetric conjugate additions of C2-symmetric chiral phosphonamide anions to cyclic enones, lacton...
Scheme 5: Asymmetric conjugate additions of P-chiral phosphonamide anions generated from 40a and 44a to cycli...
Scheme 6: Asymmetric cyclopropanation with chiral chloroallyl phosphonamide 47, mechanistic rationale, and se...
Scheme 7: Asymmetric cyclopropanation with chiral chloromethyl phosphonamide 28d [59].
Scheme 8: Stereoselective synthesis of cis-aziridines 57 from chiral chloroallyl phosphonamide 47a [62].
Scheme 9: Synthesis of phosphonamides by (A) Arbuzov reaction, (B) condensation of diamines with phosphonic a...
Figure 3: Original and revised structure of polyoxin A (69) [24-26].
Scheme 10: Synthesis of (E)-polyoximic acid (9) [24-26].
Figure 4: Key assembly strategy of acetoxycrenulide (10) [41,42].
Scheme 11: Total synthesis of (+)-acetoxycrenulide (10) [41,42].
Scheme 12: Synthesis squalene synthase inhibitor 19 by asymmetric sulfuration (A) and asymmetric alkylation (B...
Figure 5: Key assembly strategy of fumonisin B2 (20) and its tricarballylic acid fragment 105 [45,46].
Scheme 13: Final steps of the total synthesis of fumonisin B2 (20) [45,46].
Figure 6: Selected examples of two subclasses of β-lactam antibiotics – carbapenems (111 and 112) and trinems...
Scheme 14: Synthesis of tricyclic β-lactam antibiotic 123 [97].
Scheme 15: Total synthesis of (−)-anthoplalone (8) [56].
Figure 7: Protein tyrosine phosphatase (PTP) inhibitors 130, 131 and model compounds 16, 132 and 133 [68].
Scheme 16: Synthesis of model PTP inhibitors 16a,b [68].
Scheme 17: Synthesis of aziridine hydroxamic acid 17 as MMP inhibitor [63].
Scheme 18: Synthesis of methyl jasmonate (11) [48].
Figure 8: Structures of nudiflosides A (137) and D (13) [49].
Scheme 19: Total synthesis of the pentasubstituted cyclopentane core 159 of nudiflosides A (151) and D (13) an...
Figure 9: L-glutamic acid (161) and constrained analogues [57,124].
Scheme 20: Stereoselective synthesis of DCG-IV (162) [57].
Scheme 21: Stereoselective synthesis of mGluR agonist 21 [124].
Figure 10: Key assembly strategy of berkelic acid (15) [43].
Scheme 22: Total synthesis of berkelic acid (15) [43].
Figure 11: Key assembly strategy of jerangolid A (22) and ambruticin S (14) [27,28].
Scheme 23: Final assembly steps in the total synthesis of jerangolid A [27].
Scheme 24: Key assembly steps in the total synthesis of ambruticin S (14) [28].
Figure 12: General steroid construction strategy based on conjugate addition of 212 to cyclopentenone 48, exem...
Scheme 25: Total synthesis of estrone (12) [44].
Beilstein J. Org. Chem. 2014, 10, 1765–1774, doi:10.3762/bjoc.10.184
Graphical Abstract
Scheme 1: The general form of the Strecker reaction. The reaction (b) is taken from [2].
Scheme 2: The first asymmetric Strecker reaction [4].
Scheme 3: The first asymmetric synthesis of α-aminonitirles via a chiral catalyst [5].
Scheme 4: A reaction model composed of Me-CH=O, HCN, NH3 and (H2O)10 for geometry optimizations to trace elem...
Scheme 5: Possible pathways for the formation of aminonitrile from acetaldehyde.
Figure 1: Geometries of transition states along the reaction from acetaldehyde (1) to the aminonitrile 8. Dis...
Figure 2: Energy changes along elementary processes from acetaldehyde to aminonitrile. Bold numbers are defin...
Scheme 6: A short-cut path by the nucleophilic displacement and the concomitant proton transfer. “The first b...
Scheme 7: A contrast of the nucleophilic addition.
Figure 3: Two transition states (A and B) of the nucleophilic addition of (S)-α-phenylethylamine to acetaldeh...
Scheme 8: Elementary processes of the acid-catalyzed hydrolysis of 2-amino-propanonitrile.
Figure 4: Energy changes along elementary processes from 2-amino nitrile 8 to 2-amino acid 16. Brown-color li...
Figure 5: Geometries of transition states along the most favorable route from 2-aminonitrile 8 to 2-amino aci...
Scheme 9: Summary of the present computational work expressed by minimal models.
Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117
Graphical Abstract
Scheme 1: Pioneer works of Atherton, Openshaw and Todd reporting on the synthesis of phosphoramidate starting...
Scheme 2: Mechanisms 1 (i) and 2 (ii) suggested by Atherton and Todd in 1945; adapted from [1].
Scheme 3: Two reaction pathways (i and ii) to produce chlorophosphate 2. Charge-transfer complex observed whe...
Scheme 4: Mechanism of the Atherton–Todd reaction with dimethylphosphite according to Roundhill et al. (adapt...
Scheme 5: Synthesis of dialkyl phosphate from dialkyl phosphite (i) and identification of chloro- and bromoph...
Scheme 6: Synthesis of chiral phosphoramidate with trichloromethylphosphonate as the suggested intermediate (...
Scheme 7: Selection of results that address the question of the stereochemistry of the AT reaction (adapted f...
Scheme 8: Synthesis of phenoxy spirophosphorane by the AT reaction (adapted from [34]).
Scheme 9: Suggested mechanism of the Atherton–Todd reaction, (i) and (ii) formation of chlorophosphate with a...
Scheme 10: AT reaction in biphasic conditions (adapted from [38]).
Scheme 11: AT reaction with iodoform as halide source (adapted from [37]).
Scheme 12: AT reaction with phenol at low temperature in the presence of DMAP (adapted from [40]).
Scheme 13: Synthesis of a triphosphate by the AT reaction starting with the preparation of chlorophosphate (ad...
Scheme 14: AT reaction with sulfonamide (adapted from [42]).
Scheme 15: Synthesis of a styrylphosphoramidate starting from the corresponding aniline (adapted from [43]).
Scheme 16: Use of hydrazine as nucleophile in AT reactions (adapted from [48]).
Scheme 17: AT reaction with phenol as a nucleophilic species; synthesis of dioleyl phosphate-substituted couma...
Scheme 18: Synthesis of β-alkynyl-enolphosphate from allenylketone with AT reaction (adapted from [58]).
Scheme 19: Synthesis of pseudohalide phosphate by using AT reaction (adapted from [67]).
Scheme 20: AT reaction with hydrospirophosphorane with insertion of CO2 in the product (adapted from [69]).
Scheme 21: AT reaction with diaryl phosphite (adapted from [70]).
Scheme 22: AT reaction with O-alkyl phosphonite (adapted from [71]).
Scheme 23: Use of phosphinous acid in AT reactions (adapted from [72]).
Scheme 24: AT reaction with secondary phosphinethiooxide (adapted from [76]).
Scheme 25: Use of H-phosphonothioate in the AT reaction (adapted from [78]).
Scheme 26: AT-like reaction with CuI as catalyst and without halide source (adapted from [80]).
Scheme 27: Reduction of phenols after activation as phosphate derivatives (adapted from [81] i ; [82], ii; and [83], iii).
Scheme 28: Synthesis of medium and large-sized nitrogen-containing heterocycles (adapted from [85]).
Scheme 29: Synthesis of arylstannane from aryl phosphate prepared by an AT reaction (adapted from [86]).
Scheme 30: Synthesis and use of aryl dialkyl phosphate for the synthesis of biaryl derivatives (adapted from [89])....
Scheme 31: Synthesis of aryl dialkyl phosphate by an AT reaction from phenol and subsequent rearrangement yiel...
Scheme 32: Selected chiral phosphoramidates used as organocatalyst; i) chiral phosphoramidate used in the pion...
Scheme 33: Determination of ee of H-phosphinate by the application of the AT reaction with a chiral amine (ada...
Scheme 34: Chemical structure of selected flame retardants synthesized by AT reactions; (BDE: polybrominated d...
Scheme 35: Transformation of DOPO (i) and synthesis of polyphosphonate (ii) by the AT reaction (adapted from [117] ...
Scheme 36: Synthesis of lipophosphite (bisoleyl phosphite) and cationic lipophosphoramidate with an AT reactio...
Scheme 37: Use of AT reactions to produce cationic lipids characterized by a trimethylphosphonium, trimethylar...
Scheme 38: Cationic lipid synthesized by the AT reaction illustrating the variation of the structure of the li...
Scheme 39: Helper lipids for nucleic acid delivery synthesized with the AT reaction (adapted from [130]).
Scheme 40: AT reaction used to produce red/ox-sensitive cationic lipids (adapted from [135]).
Scheme 41: Alkyne and azide-functionalized phosphoramidate synthesized by AT reactions,(i); illustration of so...
Scheme 42: Cationic lipids exhibiting bactericidal action – arrows indicate the bond formed by the AT reaction...
Scheme 43: β-Cyclodextrin-based lipophosphoramidates (adapted from [138]).
Scheme 44: Polyphosphate functionalized by an AT reaction (adapted from [139]).
Scheme 45: Synthesis of zwitterionic phosphocholine-bound chitosan (adapted from [142]).
Scheme 46: Synthesis of AZT-based prodrug via an AT reaction (adapted from [143]).
Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106
Graphical Abstract
Scheme 1: Synthesis of P-stereogenic phosphines 5 using menthylphosphinite borane diastereomers 2.
Scheme 2: Enantioselective synthesis of chiral phosphines 10 with ephedrine as a chiral auxiliary.
Scheme 3: Chlorophosphine boranes 11a as P-chirogenic electrophilic building blocks.
Scheme 4: Monoalkylation of phenylphosphine borane 15 with methyl iodide in the presence of Cinchona alkaloid...
Scheme 5: Preparation of tetraphosphine borane 19.
Scheme 6: Using chiral chlorophosphine-boranes 11b as phosphide borane 20 precursors.
Scheme 7: Nickel-catalyzed cross-coupling (dppe = 1,2-bis(diphenylphosphino)ethane).
Scheme 8: Pd-catalyzed cross-coupling reaction with organophosphorus stannanes 30.
Scheme 9: Copper iodide catalyzed carbon–phosphorus bond formation.
Scheme 10: Thermodynamic kinetic resolution as the origin of enantioselectivity in metal-catalyzed asymmetric ...
Scheme 11: Ru-catalyzed asymmetric phosphination of benzyl and alkyl chlorides 35 with HPPhMe (36a, PHOX = pho...
Scheme 12: Pt-catalyzed asymmetric alkylation of secondary phosphines 36b.
Scheme 13: Different adducts 43 can result from hydrophosphination.
Scheme 14: Pt-catalyzed asymmetric hydrophosphination.
Scheme 15: Intramolecular hydrophosphination of phosphinoalkene 47.
Scheme 16: Organocatalytic asymmetric hydrophosphination of α,β-unsaturated aldehydes 59.
Scheme 17: Preparation of phosphines using zinc organometallics.
Scheme 18: Preparation of alkenylphosphines 71a from alkenylzirconocenes 69 (dtc = N,N-diethyldithiocarbamate,...
Scheme 19: SNAr with P-chiral alkylmethylphosphine boranes 13c.
Scheme 20: Synthesis of QuinoxP 74 (TMEDA = tetramethylethylenediamine).
Scheme 21: Pd-Mediated couplings of a vinyl triflate 76 with diphenylphosphine borane 13e.
Figure 1: Menthone (83) and camphor (84) derived chiral phosphines.
Scheme 22: Palladium-catalyzed cross-coupling reaction of vinyl tosylates 85 and 87 with diphenylphosphine bor...
Scheme 23: Attempt for the enantioselective palladium-catalyzed C–P cross-coupling reaction between an alkenyl...
Scheme 24: Enol phosphates 88 as vinylic coupling partners in the palladium-catalyzed C–P cross-coupling react...
Scheme 25: Nickel-catalyzed cross-coupling in the presence of zinc (dppe = 1,2-bis(diphenylphosphino)ethane).
Scheme 26: Copper-catalyzed coupling of secondary phosphines with vinyl halide 94.
Scheme 27: Palladium-catalyzed cross-coupling of aryl iodides 97 with organoheteroatom stannanes 30.
Scheme 28: Synthesis of optically active phosphine boranes 100 by cross-coupling with a chiral phosphine boran...
Scheme 29: Palladium-catalyzed P–C cross-coupling reactions between primary or secondary phosphines and functi...
Scheme 30: Enantioselective synthesis of a P-chirogenic phosphine 108.
Scheme 31: Enantioselective arylation of silylphosphine 110 ((R,R)-Et-FerroTANE = 1,1'-bis((2R,4R)-2,4-diethyl...
Scheme 32: Nickel-catalyzed arylation of diphenylphosphine 25d.
Scheme 33: Nickel-catalyzed synthesis of (R)-BINAP 116 (dppe = 1,2-bis(diphenylphosphino)ethane, DABCO = 1,4-d...
Scheme 34: Nickel-catalyzed cross-coupling between aryl bromides 119 and diphenylphosphine (25d) (dppp = 1,3-b...
Scheme 35: Stereocontrolled Pd(0)−Cu(I) cocatalyzed aromatic phosphorylation.
Scheme 36: Preparation of alkenylphosphines by hydrophosphination of alkynes.
Scheme 37: Palladium and nickel-catalyzed addition of P–H to alkynes 125a.
Scheme 38: Palladium-catalyzed asymmetric hydrophosphination of an alkyne 128.
Scheme 39: Ruthenium catalyzed hydrophosphination of propargyl alcohols 132 (cod = 1,5-cyclooctadiene).
Scheme 40: Cobalt-catalyzed hydrophosphination of alkynes 134a (acac = acetylacetone).
Scheme 41: Tandem phosphorus–carbon bond formation–oxyfunctionalization of substituted phenylacetylenes 125c (...
Scheme 42: Organolanthanide-catalyzed intramolecular hydrophosphination/cyclization of phosphinoalkynes 143.
Scheme 43: Hydrophosphination of alkynes 134c catalyzed by ytterbium-imine complexes 145 (hmpa = hexamethylpho...
Scheme 44: Calcium-mediated hydrophosphanylation of alkyne 134d.
Scheme 45: Formation and substitution of bromophosphine borane 151.
Scheme 46: General scheme for a nickel or copper catalyzed cross-coupling reaction.
Scheme 47: Copper-catalyzed synthesis of alkynylphosphines 156.
Beilstein J. Org. Chem. 2014, 10, 784–793, doi:10.3762/bjoc.10.74
Graphical Abstract
Scheme 1: Reactions of furan-2,3-diones 1 and azirines 2.
Figure 1: Molecular structures of compounds 3а, 4b.
Scheme 2: The route of formation of compounds 3 and possible intermediates in route to compounds 4 and 5.
Figure 2: Energy profiles for the reactions of azirines 2a,c and acylketene 6a, as well as acylketene 6a with...
Scheme 3: Possible intermediates in routes to compounds 4 and 5.
Figure 3: Energy profiles for the reactions of dihydropyrazine 11a with acylketene 6a, as well as acylketene ...
Figure 4: Energy profiles for the reactions of azirines 2a,c with protonated azirines 14a,c. Relative free en...
Scheme 4: Isodesmic equation for evaluation of relative basicity of azirines 2c,a.
Scheme 5: Reaction of furandione 1a with azirine 2d.
Figure 5: Molecular structure of compound 17.
Scheme 6: Reaction of furandione 1d with azirine 2a.
Scheme 7: Reactions of compounds 3d and 18a with methanol.
Beilstein J. Org. Chem. 2014, 10, 752–760, doi:10.3762/bjoc.10.70
Graphical Abstract
Scheme 1: Preparation of enol ethers.
Scheme 2: Reaction of enol ethers with hydrazine hydrate.
Scheme 3: Pyrazoles 5.
Figure 1: Tautomers of 5a.
Figure 2: Tautomers of 5b (R = Me), 5c (R = Et).
Figure 3: Tautomers of 5b (R = Me), 5c (R = Et).
Figure 4: Tautomers of 5d.
Scheme 4: Reactions of hydrazine hydrate with dialkyl alkoxymethylidenemalonates.
Figure 5: Crystal structure and crystal packing of compound 6a.
Figure 6: Key 1H (red), 13C (black) and 15N (blue) NMR chemical shifts (δ, ppm) in isomers A and B of compoun...
Figure 7: DFT optimized isomers of compound 6a. (Distances are in Å, angles are in degrees.)
Beilstein J. Org. Chem. 2014, 10, 641–652, doi:10.3762/bjoc.10.56
Graphical Abstract
Figure 1: Raspberry Pi® (RPi) computer operating in the laboratory, shown here without its protective case. U...
Figure 2: Two step approach to piperazine-2-carboxamide via hydrolysis followed by reduction. (a) Retrosynthe...
Figure 3: Heterogeneous hydration of pyrazine-2-carbonitrile with hydrous zirconia.
Figure 4: FlowIR™ profile for the reactor output after hydration of pyrazine-2-carbonitrile using hydrous zir...
Figure 5: (a) Fluidic setup for the zirconia catalysed hydration of aromatic nitrile. (b) Raspberry Pi® micro...
Figure 6: Flowchart describing the control sequence for operating and monitoring the hydration reaction. The ...
Figure 7: Profile for a 3 hour reaction simulating a long run. The absorbance shown is that at 1685 cm−1, whi...
Figure 8: Reactor setup for optimisation reactions. A multi-position valve (V2) was used for collecting sampl...
Figure 9: Representation of the control sequence for running experiments under a set of conditions. (See Supporting Information File 3 for...
Figure 10: Reduction products of piperazine-2-carboxamide.
Figure 11: (a) In-line reservoir schematic. The liquid level is measured by observation of a plastic float. (b...
Figure 12: Flow set up for the automated machine assisted synthesis of (R,S)-piperidine-2-carboxamide.
Figure 13: Control sequence for the two-step process.
Figure 14: Chart of monitored parameters over a 15 hour reaction. The output from the hydrolysis step is direc...
Beilstein J. Org. Chem. 2014, 10, 544–598, doi:10.3762/bjoc.10.50
Graphical Abstract
Scheme 1: The proposed mechanism of the Passerini reaction.
Scheme 2: The PADAM-strategy to α-hydroxy-β-amino amide derivatives 7. An additional oxidation provides α-ket...
Scheme 3: The general accepted Ugi-mechanism.
Scheme 4: Three commonly applied Ugi/cyclization approaches. a) UDC-process, b) UAC-sequence, c) UDAC-combina...
Scheme 5: Ugi reaction that involves the condensation of Armstrong’s convertible isocyanide.
Scheme 6: Mechanism of the U-4C-3CR towards bicyclic β-lactams.
Scheme 7: The Ugi 4C-3CR towards oxabicyclo β-lactams.
Scheme 8: Ugi MCR between an enantiopure monoterpene based β-amino acid, aldehyde and isocyanide resulting in...
Scheme 9: General MCR for β-lactams in water.
Scheme 10: a) Ugi reaction for β-lactam-linked peptidomimetics. b) Varying the β-amino acid resulted in β-lact...
Scheme 11: Ugi-4CR followed by a Pd-catalyzed Sn2 cyclization.
Scheme 12: Ugi-3CR of dipeptide mimics from 2-substituted pyrrolines.
Scheme 13: Joullié–Ugi reaction towards 2,5-disubstituted pyrrolidines.
Scheme 14: Further elaboration of the Ugi-scaffold towards bicyclic systems.
Scheme 15: Dihydroxyproline derivatives from an Ugi reaction.
Scheme 16: Diastereoselective Ugi reaction described by Banfi and co-workers.
Scheme 17: Similar Ugi reaction as in Scheme 16 but with different acids and two chiral isocyanides.
Scheme 18: Highly diastereoselective synthesis of pyrrolidine-dipeptoids via a MAO-N/MCR-procedure.
Scheme 19: MAO-N/MCR-approach towards the hepatitis C drug telaprevir.
Scheme 20: Enantioselective MAO-U-3CR procedure starting from chiral pyrroline 64.
Scheme 21: Synthesis of γ-lactams via an UDC-sequence.
Scheme 22: Utilizing bifunctional groups to provide bicyclic γ-lactam-ketopiperazines.
Scheme 23: The Ugi reaction provided both γ- as δ-lactams depending on which inputs were used.
Scheme 24: The sequential Ugi/RCM with olefinic substrates provided bicyclic lactams.
Scheme 25: a) The structural and dipole similarities of the triazole unit with the amide bond. b) The copper-c...
Scheme 26: The Ugi/Click sequence provided triazole based peptidomimetics.
Scheme 27: The Ugi/Click reaction as described by Nanajdenko.
Scheme 28: The Ugi/Click-approach by Pramitha and Bahulayan.
Scheme 29: The Ugi/Click-combination by Niu et al.
Scheme 30: Triazole linked peptidomimetics obtained from two separate MCRs and a sequential Click reaction.
Scheme 31: Copper-free synthesis of triazoles via two MCRs in one-pot.
Scheme 32: The sequential Ugi/Paal–Knorr reaction to afford pyrazoles.
Scheme 33: An intramolecular Paal–Knorr condensation provided under basic conditions pyrazolones.
Scheme 34: Similar cyclization performed under acidic conditions provided pyrazolones without the trifluoroace...
Scheme 35: The Ugi-4CR towards 2,4-disubstituted thiazoles.
Scheme 36: Solid phase approach towards thiazoles.
Scheme 37: Reaction mechanism of formation of thiazole peptidomimetics containing an additional β-lactam moiet...
Scheme 38: The synthesis of the trisubstituted thiazoles could be either performed via an Ugi reaction with pr...
Scheme 39: Performing the Ugi reaction with DMB-protected isocyanide gave access to either oxazoles or thiazol...
Scheme 40: Ugi/cyclization-approach towards 2,5-disubstituted thiazoles. The Ugi reaction was performed with d...
Scheme 41: Further derivatization of the thiazole scaffold.
Scheme 42: Three-step procedure towards the natural product bacillamide C.
Scheme 43: Ugi-4CR to oxazoles reported by Zhu and co-workers.
Scheme 44: Ugi-based synthesis of oxazole-containing peptidomimetics.
Scheme 45: TMNS3 based Ugi reaction for peptidomimics containing a tetrazole.
Scheme 46: Catalytic cycle of the enantioselective Passerini reaction towards tetrazole-based peptidomimetics.
Scheme 47: Tetrazole-based peptidomimetics via an Ugi reaction and a subsequent sigmatropic rearrangement.
Scheme 48: Resin-bound Ugi-approach towards tetrazole-based peptidomimetics.
Scheme 49: Ugi/cyclization approach towards γ/δ/ε-lactam tetrazoles.
Scheme 50: Ugi-3CR to pipecolic acid-based peptidomimetics.
Scheme 51: Staudinger–Aza-Wittig/Ugi-approach towards pipecolic acid peptidomimetics.
Figure 1: The three structural isomers of diketopiperazines. The 2,5-DKP isomer is most common.
Scheme 52: UDC-approach to obtain 2,5-DKPs, either using Armstrong’s isocyanide or via ethylglyoxalate.
Scheme 53: a) Ugi reaction in water gave either 2,5-DKP structures or spiro compounds. b) The Ugi reaction in ...
Scheme 54: Solid-phase approach towards diketopiperazines.
Scheme 55: UDAC-approach towards DKPs.
Scheme 56: The intermediate amide is activated as leaving group by acid and microwave assisted organic synthes...
Scheme 57: UDC-procedure towards active oxytocin inhibitors.
Scheme 58: An improved stereoselective MCR-approach towards the oxytocin inhibitor.
Scheme 59: The less common Ugi reaction towards DKPs, involving a Sn2-substitution.
Figure 2: Spatial similarities between a natural β-turn conformation and a DKP based β-turn mimetic [158].
Scheme 60: Ugi-based syntheses of bicyclic DKPs. The amine component is derived from a coupling between (R)-N-...
Scheme 61: Ugi-based synthesis of β-turn and γ-turn mimetics.
Figure 3: Isocyanide substituted 3,4-dihydropyridin-2-ones, dihydropyridines and the Freidinger lactams. Bio-...
Scheme 62: The mechanism of the 4-CR towards 3,4-dihydropyridine-2-ones 212.
Scheme 63: a) Multiple MCR-approach to provide DHP-peptidomimetic in two-steps. b) A one-pot 6-CR providing th...
Scheme 64: The MCR–alkylation–MCR procedure to obtain either tetrapeptoids or depsipeptides.
Scheme 65: U-3CR/cyclization employing semicarbazone as imine component gave triazine based peptidomimetics.
Scheme 66: 4CR towards triazinane-diones.
Scheme 67: The MCR–alkylation–IMCR-sequence described by our group towards triazinane dione-based peptidomimet...
Scheme 68: Ugi-4CR approaches followed by a cyclization to thiomorpholin-ones (a) and pyrrolidines (b).
Scheme 69: UDC-approach for benzodiazepinones.
Scheme 70: Ugi/Mitsunobu sequence to BDPs.
Scheme 71: A UDAC-approach to BDPs with convertible isocyanides. The corresponding amide is cleaved by microwa...
Scheme 72: microwave assisted post condensation Ugi reaction.
Scheme 73: Benzodiazepinones synthesized via the post-condensation Ugi/ Staudinger–Aza-Wittig cyclization.
Scheme 74: Two Ugi/cyclization approaches utilizing chiral carboxylic acids. Reaction (a) provided the product...
Scheme 75: The mechanism of the Gewald-3CR includes three base-catalysed steps involving first a Knoevnagel–Co...
Scheme 76: Two structural 1,4-thienodiazepine-2,5-dione isomers by U-4CR/cyclization.
Scheme 77: Tetrazole-based diazepinones by UDC-procedure.
Scheme 78: Tetrazole-based BDPs via a sequential Ugi/hydrolysis/coupling.
Scheme 79: MCR synthesis of three different tricyclic BPDs.
Scheme 80: Two similar approaches both involving an Ugi reaction and a Mitsunobu cyclization.
Scheme 81: Mitsunobu–Ugi-approach towards dihydro-1,4-benzoxazepines.
Scheme 82: Ugi reaction towards hetero-aryl fused 5-oxo-1,4-oxazepines.
Scheme 83: a) Ugi/RCM-approach towards nine-membered peptidomimetics b) Sequential peptide-coupling, deprotect...
Scheme 84: Ugi-based synthesis towards cyclic RGD-pentapeptides.
Scheme 85: Ugi/MCR-approach towards 12–15 membered macrocycles.
Scheme 86: Stereoselective Ugi/RCM approach towards 16-membered macrocycles.
Scheme 87: Passerini/RCM-sequence to 22-membered macrocycles.
Scheme 88: UDAC-approach towards 12–18-membered depsipeptides.
Figure 4: Enopeptin A with its more active derivative ADEP-4.
Scheme 89: a) The Joullié–Ugi-approach towards ADEP-4 derivatives b) Ugi-approach for the α,α-dimethylated der...
Scheme 90: Ugi–Click-strategy for 15-membered macrocyclic glyco-peptidomimetics.
Scheme 91: Ugi/Click combinations provided macrocycles containing both a triazole and an oxazole moiety.
Scheme 92: a) A solution-phase procedure towards macrocycles. b) Alternative solid-phase synthesis as was repo...
Scheme 93: Ugi/cyclization towards cyclophane based macrocycles.
Scheme 94: PADAM-strategy towards eurystatin A.
Scheme 95: PADAM-approach for cyclotheanamide.
Scheme 96: A triple MCR-approach affording RGD-pentapeptoids.
Scheme 97: Ugi-MiBs-approach towards peptoid macrocycles.
Scheme 98: Passerini-based MiB approaches towards macrocycles 345 and 346.
Scheme 99: Macrocyclic peptide formation by the use of amphoteric aziridine-based aldehydes.
Beilstein J. Org. Chem. 2014, 10, 466–470, doi:10.3762/bjoc.10.44
Graphical Abstract
Scheme 1: Synthesis and conversion of 3,4-dihydro-2H-pyrrole-2-carbonitriles 6.
Beilstein J. Org. Chem. 2014, 10, 394–404, doi:10.3762/bjoc.10.37
Graphical Abstract
Scheme 1: Flögel-three-component reaction of lithiated alkoxyallenes, nitriles and carboxylic acids providing...
Scheme 2: Synthesis of bis(β-ketoenamides) 13–15 by three-component reactions of lithiated methoxyallene 8 wi...
Scheme 3: Cyclocondensations of β-ketoenamides 13 and 14 to 4-hydroxypyridines 16, 18a and 18b, their subsequ...
Scheme 4: Cyclocondensations of β-ketoenamides 13–15 with ammonium acetate to bis(pyrimidine) derivatives 23a...
Scheme 5: Conversion of mono-pyrimidine derivative 24b into unsymmetrically substituted biphenylen-bridged py...
Scheme 6: Condensation of β-ketoenamides 14 and 20 with hydroxylamine hydrochloride to pyridine-N-oxides 28 a...
Scheme 7: Riley oxidation of bis(pyrimidine) derivative 23a and conversion of diol 32a into macrocycle 34.
Figure 1: Optimized geometries of (a) E-configured and (b) Z-configured macrocycle 34 at B3LYP/6-31G(d,p) lev...
Scheme 8: Dihydroxylation of the macrocyclic olefin 34 to diol 35 and subsequent esterification to the bis-(R...
Beilstein J. Org. Chem. 2014, 10, 163–193, doi:10.3762/bjoc.10.14
Graphical Abstract
Scheme 1: Vogel’s first approach towards the divinylcyclopropane rearrangement [4] and characterization of cis-d...
Scheme 2: Transition states for the Cope rearrangement and the related DVCPR. Ts = transition state.
Scheme 3: Two possible mechanisms of trans-cis isomerizations of divinylcyclopropanes.
Scheme 4: Proposed biosynthesic pathway to ectocarpene (21), an inactive degradation product of a sexual pher...
Scheme 5: Proposed biosynthesis of occidenol (25) and related natural compounds.
Scheme 6: Gaich’s bioinspired system using the DVCPR to mimick the dimethylallyltryptophan synthase. DMAPP = ...
Scheme 7: Iguchi’s total synthesis of clavubicyclone, part 1.
Scheme 8: Iguchi’s total synthesis of clavubicyclone, part 2.
Scheme 9: Wender’s syntheses of the two pseudoguainanes confertin (50) and damsinic acid (51) and Pier’s appr...
Scheme 10: Overman’s total synthesis of scopadulcic acid B.
Scheme 11: Davies’ total syntheses of tremulenolide A and tremulenediol A.
Scheme 12: Davies formal [4 + 3] cycloaddition approach towards the formal synthesis of frondosin B.
Scheme 13: Davies and Sarpongs formal [4 + 3]-cycloaddition approach towards barekoxide (106) and barekol (107...
Scheme 14: Davies formal [4 + 3]-cycloaddition approach to 5-epi-vibsanin E (115) containing an intermediate c...
Scheme 15: Echavarren’s total synthesis of schisanwilsonene A (126) featuring an impressive gold-catalzed casc...
Scheme 16: Davies early example of a formal [4 + 3]-cycloaddition in alkaloids synthesis.
Scheme 17: Fukuyama’s total synthesis of gelsemine, part 1.
Scheme 18: Fukuyama’s total synthesis of gelsemine, featuring a divinylcyclopropane rearrangement, part 2.
Scheme 19: Kende’s total synthesis of isostemofoline, using a formal [4 + 3]-cycloaddition, including an inter...
Scheme 20: Danishefsky’s total synthesis of gelsemine, part 1.
Scheme 21: Danishefsky’s total synthesis of gelsemine, part 2.
Scheme 22: Fukuyama’s total synthesis of gelsemoxonine.
Scheme 23: Wender’s synthetic access to the core skeleton of tiglianes, daphnanes and ingenanes.
Scheme 24: Davies’ approach towards the core skeleton of CP-263,114 (212).
Scheme 25: Wood’s approach towards actinophyllic acid.
Scheme 26: Takeda’s approach towards the skeleton of the cyanthins, utilitizing the divinylcyclopropane rearra...
Scheme 27: Donaldson’s organoiron route towards the guianolide skeleton.
Scheme 28: Stoltz’s tandem Wolff/DVCPR rearrangement.
Scheme 29: Stephenson’s tandem photocatalysis/arylvinylcyclopropane rearrangement.
Scheme 30: Padwa’s rhodium cascade involving a DVCPR.
Scheme 31: Matsubara’s version of a DVCPR.
Scheme 32: Toste’s tandem gold-catalyzed Claisen-rearrangement/DVCPR.
Scheme 33: Ruthenium- and gold-catalyzed versions of tandem reactions involving a DVCPR.
Scheme 34: Tungsten, platinum and gold catalysed cycloisomerizations leading to a DVCPR.
Scheme 35: Reisman’s total synthesis of salvileucalin B, featuring an (undesired) vinylcyclopropyl carbaldehyd...
Scheme 36: Studies on the divinylepoxide rearrangement.
Scheme 37: Studies on the vinylcyclopropanecarbonyl rearrangement.
Scheme 38: Nitrogen-substituted variants of the divinylcyclopropane rearrangement.
Beilstein J. Org. Chem. 2013, 9, 2586–2614, doi:10.3762/bjoc.9.294
Graphical Abstract
Figure 1: Elementary steps in the gold-catalyzed nucleophilic addition to olefins.
Figure 2: Different approaches for the gold-catalyzed manipulation of inactivated alkenes.
Figure 3: Computed mechanistic cycle for the gold-catalyzed alkoxylation of ethylene with PhOH.
Scheme 1: [Au(I)]-catalyzed addition of phenols and carboxylic acids to alkenes.
Scheme 2: [Au(III)] catalyzed annulations of phenols and naphthols with dienes.
Scheme 3: [Au(III)]-catalyzed addition of aliphatic alcohols to alkenes.
Scheme 4: [Au(III)]-catalyzed carboalkoxylation of alkenes with dimethyl acetals 6.
Figure 4: Postulated mechanism for the [Au(I)]-catalyzed hydroamination of olefins.
Scheme 5: Isolation and reactivity of alkyl gold intermediates in the intramolecular hydroamination of alkene...
Scheme 6: [Au(I)]-catalyzed intermolecular hydroamination of dienes.
Scheme 7: Intramolecular [Au(I)]-catalyzed hydroamination of alkenes with carbamates.
Scheme 8: [Au(I)]-catalyzed inter- as well as intramolecular addition of sulfonamides to isolated alkenes.
Scheme 9: Intramolecular hydroamination of N-alkenylureas catalyzed by gold(I) carbene complex.
Scheme 10: Enantioselective hydroamination of alkenyl ureas with biphenyl tropos ligand and chiral silver phos...
Scheme 11: Intramolecular [Au(I)]-catalyzed hydroamination of N-allyl-N’-aryl ureas. (PNP = pNO2-C6H4, PMP = p...
Scheme 12: [Au(I)]-catalyzed hydroamination of alkenes with ammonium salts.
Scheme 13: Enantioselective [Au(I)]-catalyzed intermolecular hydroamination of alkenes with cyclic ureas.
Scheme 14: Mechanistic proposal for the cooperative [Au(I)]/menthol catalysis for the enantioselective intramo...
Scheme 15: [Au(III)]-catalyzed addition of 1,3-diketones to alkenes.
Scheme 16: [Au(I)]-catalyzed intramolecular addition of β-keto amides to alkenes.
Scheme 17: Intermolecular [Au(I)]-catalyzed addition of indoles to alkenes.
Scheme 18: Intermolecular [Au(III)]-catalyzed hydroarylation of alkenes with benzene derivatives and thiophene....
Scheme 19: a) Intramolecular [Au(III)]-catalyzed hydroarylation of alkenes. b) A SEAr-type mechanism was hypot...
Scheme 20: Intramolecular [Au(I)]-catalyzed hydroalkylation of alkenes with simple ketones.
Scheme 21: Proposed reaction mechanism for the intramolecular [Au(I)]-catalyzed hydroalkylation of alkenes wit...
Scheme 22: Tandem Michael addition/hydroalkylation catalyzed by [Au(I)] and [Ag(I)] salts.
Scheme 23: Intramolecular [Au(I)]-catalyzed tandem migration/[2 + 2] cycloaddition of 1,7-enyne benzoates.
Scheme 24: Intramolecular [Au(I)]-catalyzed cyclopropanation of alkenes.
Scheme 25: Stereospecificity in [Au(I)]-catalyzed hydroalkoxylation of allylic alcohols.
Scheme 26: Mechanistic investigation on the intramolecular [Au(I)]-catalyzed hydroalkoxylation of allylic alco...
Scheme 27: Mechanistic investigation on the intramolecular enantioselective [Au(I)]-catalyzed alkylation of in...
Scheme 28: Synthesis of (+)-isoaltholactone via stereospecific intramolecular [Au(I)]-catalyzed alkoxylation o...
Scheme 29: Intramolecular enantioselective dehydrative amination of allylic alcohols catalyzed by chiral [Au(I...
Scheme 30: Enantioselective intramolecular hydroalkylation of allylic alcohols with aldehydes catalyzed by 20c...
Scheme 31: Gold-catalyzed intramolecular diamination of alkenes.
Scheme 32: Gold-catalyzed aminooxygenation and aminoarylation of alkenes.
Scheme 33: Gold-catalyzed carboamination, carboalkoxylation and carbolactonization of terminal alkenes with ar...
Scheme 34: Synthesis of tricyclic indolines via gold-catalyzed formal [3 + 2] cycloaddition.
Scheme 35: Gold(I) catalyzed aminoarylation of terminal alkenes in presence of Selectfluor [dppm = bis(dipheny...
Scheme 36: Mechanistic investigation on the aminoarylation of terminal alkenes by bimetallic gold(I) catalysis...
Scheme 37: Proposed mechanism for the aminoarylation of alkenes via [Au(I)-Au(I)]/[Au(II)-Au(II)] redox cataly...
Scheme 38: Oxyarylation of terminal olefins via redox gold catalysis.
Scheme 39: a) Intramolecular gold-catalyzed oxidative coupling reactions with aryltrimethylsilanes. b) Oxyaryl...
Scheme 40: Oxy- and amino-arylation of alkenes by [Au(I)]/[Au(III)] photoredox catalysis.
Beilstein J. Org. Chem. 2013, 9, 2404–2409, doi:10.3762/bjoc.9.277
Graphical Abstract
Figure 1: Copper-catalyzed trifluoromethylation of various aryl iodides. Yields were determined by 19F NMR an...
Scheme 1: Observation of CuCF3 species in 19F NMR spectrum. aEquivalents based on Zn(CF3)I. bYields based on ...
Scheme 2: Proposed mechanism of copper-catalyzed trifluoromethylation.