Search for "halide" in Full Text gives 359 result(s) in Beilstein Journal of Organic Chemistry. Showing first 200.
Beilstein J. Org. Chem. 2024, 20, 1286–1291, doi:10.3762/bjoc.20.111
Graphical Abstract
Scheme 1: (a) Oxidative hydrolysis of styrene or stilbene type haloalkenes. (b) Fate of unsymmetrical dialkyl...
Scheme 2: Substrate scope. Unless otherwise stated 0.2 mmol of 1 was used and the isolated yields are given.
Scheme 3: Proposed catalytic cycle.
Beilstein J. Org. Chem. 2024, 20, 1278–1285, doi:10.3762/bjoc.20.110
Graphical Abstract
Scheme 1: Overview of the synthesis of compounds 1–63.
Figure 1: Temperature-dependent viscosity measurement of NTf2− TAAILs 37–63 with a butyl chain and different ...
Figure 2: Conductivity of NTf2− TAAILs 37–63 measured at 25 °C. Compounds 48, 51, and 54 are excluded because...
Figure 3: Conductivity of NTf2− TAAILs with a butyl chain plotted against their viscosity at 25 °C.
Figure 4: Linear sweep voltammetry of NTf2− TAAILs with a butyl chain and different aryl substituents R. Blac...
Figure 5: Structures of the imidazolium cations obtained by DFT calculations (B3LYP/6-311++G (d,p)). The elec...
Beilstein J. Org. Chem. 2024, 20, 1256–1269, doi:10.3762/bjoc.20.108
Graphical Abstract
Scheme 1: Structures of carbonyl compounds 1, 2, 3, and 4, dianion 7, phosphorane 8 and synthesis of 1,3-bis(...
Scheme 2: Structures of chromones with different substituents located at carbon C-3 and atom numbering scheme...
Scheme 3: Synthesis of 17. Conditions: i, DBU (1.3 equiv), THF, 20 °C, 12 h.
Scheme 4: Synthesis of 18a–ac. Conditions: i, 1) 9a–j, Me3SiOTf (1.3 equiv), 20 °C, 1 h; 2) 6a–h (1.3 equiv),...
Scheme 5: Synthesis of 19a–d. Conditions: i, DBU (1.3 equiv), THF, 20 °C, 12 h.
Scheme 6: Synthesis of 20a–ag. Conditions: i, 1) 10a–i, Me3SiOTf (0.3 equiv), 20 °C, 10 min; 2) 6a–h (1.3 equ...
Scheme 7: Synthesis of 21a–g. Conditions: i, DBU (1.3 equiv), dioxane, 20 °C, 12 h.
Scheme 8: Synthesis of 22a,b. Conditions: i, DBU (1.3 equiv), dioxane, 20 °C, 12 h.
Scheme 9: Synthesis of 23a–j. Conditions: i, 1) 11a–c, Me3SiOTf (0.3 equiv), 20 °C, 1 h; 2) 6a–h (1.3 equiv),...
Scheme 10: Synthesis of 24a–w. Conditions: i, 1) 13a–c, Me3SiOTf (0.3 equiv), 20 °C, 1 h; 2) 6a–r (1.3 equiv),...
Scheme 11: Synthesis of 25a–f. Conditions: i, DBU (1.3 equiv), dioxane, 20 °C, 12 h.
Scheme 12: Synthesis of 26a–e. Conditions: i, DBU (1.3 equiv), dioxane, 20 °C, 12 h.
Scheme 13: Synthesis of 27a–c. Conditions: i, DBU (1.3 equiv), dioxane, 20 °C, 12 h.
Scheme 14: Synthesis of 28a–c. Conditions: i, DBU (1.3 equiv), dioxane, 20 °C, 12 h.
Scheme 15: Synthesis of 29a–n and 30. Conditions: i, DBU (1.3 equiv), dioxane, 20 °C, 12 h; ii, 1) KOH, MeOH; ...
Scheme 16: Synthesis of 32a,b. Conditions: i, 1) 31, Me3SiOTf (2.0 equiv), 20 °C, 1 h; 2) 6a,b (3.0 equiv), CH2...
Scheme 17: Synthesis of 33. Conditions: i, DBU (1.3 equiv), THF, 20 °C, 12 h.
Scheme 18: Synthesis of 35a–x. Conditions: i, DBU (1.3 equiv), 1,4-dioxane, 20 °C, 12 h.
Scheme 19: Synthesis of 36a–f. Conditions: i, 1) DBU (1.3 equiv), 1,4-dioxane, 20 °C, 12 h; 2) I2 (2 equiv), D...
Scheme 20: Synthesis of 37a,b. Conditions: i, 1) DBU (1.3 equiv), 1,4-dioxane, 20 °C, 12 h; 2) I2 (2 equiv), D...
Scheme 21: Synthesis of 39a–i. Conditions: i, method A: DBU (1.3 equiv), 1,4-dioxane, 20 °C; method B: K2CO3 (...
Scheme 22: Synthesis of 40. Conditions: i, piperidine, MeOH, CHCl3, reflux, 3 h.
Scheme 23: Synthesis of 41a–am. Conditions: i, Me3SiOTf, CH2Cl2, 20 °C, 12 h, then: HCl (10%); ii, NEt3, EtOH ...
Scheme 24: Synthesis of 43a–aa and 44a–ac. Conditions: i, Me3SiOTf, CH2Cl2, 20 °C, 12 h, then: HCl (10%); ii, ...
Beilstein J. Org. Chem. 2024, 20, 1076–1087, doi:10.3762/bjoc.20.95
Graphical Abstract
Figure 1: Comparison between the light-initiated radical halogenation of toluene (right), and the Ar-SE bromi...
Figure 2: Toluene halogenation mediated by NBS in absence (left) or exposed to light (right).
Figure 3: Scifinder® reaction hits for the structure “as drawn” (January 2024).
Figure 4: Yields obtained in the preparation of aryl-cored halides.
Beilstein J. Org. Chem. 2024, 20, 973–1000, doi:10.3762/bjoc.20.87
Graphical Abstract
Scheme 1: Pd(0)-catalyzed domino C,N-coupling/carbonylation/Suzuki coupling reaction for the synthesis of 2-a...
Scheme 2: Pd(0)-catalyzed single isonitrile insertion: synthesis of 1-(3-amino)-1H-indol-2-yl)-1-ketones.
Scheme 3: Pd(0)-catalyzed gas-free carbonylation of 2-alkynylanilines to 1-(1H-indol-1-yl)-2-arylethan-1-ones....
Scheme 4: Pd(II)-catalyzed heterocyclization/alkoxycarbonylation of 2-alkynylaniline imines.
Scheme 5: Pd(II)-catalyzed heterocyclization/alkoxycarbonylation of 2-alkynylanilines to N-substituted indole...
Scheme 6: Synthesis of indol-2-acetic esters by Pd(II)-catalyzed carbonylation of 1-(2-aminoaryl)-2-yn-1-ols.
Scheme 7: Pd(II)-catalyzed carbonylative double cyclization of suitably functionalized 2-alkynylanilines to 3...
Scheme 8: Indole synthesis by deoxygenation reactions of nitro compounds reported by Cenini et al. [21].
Scheme 9: Indole synthesis by reduction of nitro compounds: approach reported by Watanabe et al. [22].
Scheme 10: Indole synthesis from o-nitrostyrene compounds as reported by Söderberg and co-workers [23].
Scheme 11: Synthesis of fused indoles (top) and natural indoles present in two species of European Basidiomyce...
Scheme 12: Synthesis of 1,2-dihydro-4(3H)-carbazolones through N-heteroannulation of functionalized 2-nitrosty...
Scheme 13: Synthesis of indoles from o-nitrostyrenes by using Pd(OAc)2 and Pd(tfa)2 in conjunction with bident...
Scheme 14: Synthesis of substituted 3-alkoxyindoles via palladium-catalyzed reductive N-heteroannulation.
Scheme 15: Synthesis of 3-arylindoles by palladium-catalyzed C–H bond amination via reduction of nitroalkenes.
Scheme 16: Synthesis of 2,2′-bi-1H-indoles, 2,3′-bi-1H-indoles, 3,3′-bi-1H-indoles, indolo[3,2-b]indoles, indo...
Scheme 17: Pd-catalyzed reductive cyclization of 1,2-bis(2-nitrophenyl)ethene and 1,1-bis(2-nitrophenyl)ethene...
Scheme 18: Flow synthesis of 2-substituted indoles by reductive carbonylation.
Scheme 19: Pd-catalyzed synthesis of variously substituted 3H-indoles from nitrostyrenes by using Mo(CO)6 as C...
Scheme 20: Synthesis of indoles from substituted 2-nitrostyrenes (top) and ω-nitrostyrenes (bottom) via reduct...
Scheme 21: Synthesis of indoles from substituted 2-nitrostyrenes with formic acid as CO source.
Scheme 22: Ni-catalyzed carbonylative cyclization of 2-nitroalkynes and aryl iodides (top) and the Ni-catalyze...
Scheme 23: Mechanism of the Ni-catalyzed carbonylative cyclization of 2-nitroalkynes and aryl iodides (top) an...
Scheme 24: Route to indole derivatives through Rh-catalyzed benzannulation of heteroaryl propargylic esters fa...
Scheme 25: Pd-catalyzed cyclization of 2-(2-haloaryl)indoles reported by Yoo and co-workers [54], Guo and co-worke...
Scheme 26: Approach for the synthesis of 6H-isoindolo[2,1-a]indol-6-ones reported by Huang and co-workers [57].
Scheme 27: Zhou group’s method for the synthesis of 6H-isoindolo[2,1-a]indol-6-ones.
Scheme 28: Synthesis of 6H-isoindolo[2,1-a]indol-6-ones from o-1,2-dibromobenzene and indole derivatives by us...
Scheme 29: Pd(OAc)2-catalyzed Heck cyclization of 2-(2-bromophenyl)-1-alkyl-1H-indoles reported by Guo et al. [55]....
Scheme 30: Synthesis of indolo[1,2-a]quinoxalinone derivatives through Pd/Cu co-catalyzed carbonylative cycliz...
Scheme 31: Pd-catalyzed carbonylative cyclization of o-indolylarylamines and N-monosubstituted o-indolylarylam...
Scheme 32: Pd-catalyzed diasteroselective carbonylative cyclodearomatization of N-(2-bromobenzoyl)indoles with...
Scheme 33: Pd(0)-catalyzed synthesis of CO-linked heterocyclic scaffolds from alkene-indole derivatives and 2-...
Scheme 34: Proposed mechanism for the Pd(0)-catalyzed synthesis of CO-linked heterocyclic scaffolds.
Scheme 35: Pd-catalyzed C–H and N–H alkoxycarbonylation of indole derivatives to indole-3-carboxylates and ind...
Scheme 36: Rh-catalyzed C–H alcoxycarbonylation of indole derivatives to indole-3-carboxylates reported by Li ...
Scheme 37: Pd-catalyzed C–H alkoxycarbonylation of indole derivatives with alcohols and phenols to indole-3-ca...
Scheme 38: Synthesis of N-methylindole-3-carboxylates from N-methylindoles and phenols through metal-catalyst-...
Scheme 39: Synthesis of indol-3-α-ketoamides (top) and indol-3-amides (bottom) via direct double- and monoamin...
Scheme 40: The direct Sonogashira carbonylation coupling reaction of indoles and alkynes via Pd/CuI catalysis ...
Scheme 41: Synthesis of indole-3-yl aryl ketones reported by Zhao and co-workers [73] (path a) and Zhang and co-wo...
Scheme 42: Pd-catalyzed carbonylative synthesis of BIMs from aryl iodides and N-substituted and NH-free indole...
Scheme 43: Cu-catalyzed direct double-carbonylation and monocarbonylation of indoles and alcohols with hexaket...
Scheme 44: Rh-catalyzed direct C–H alkoxycarbonylation of indoles to indole-2-carboxylates [79] (top) and Co-catal...
Scheme 45: Pd-catalyzed carbonylation of NH free-haloindoles.
Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72
Graphical Abstract
Scheme 1: Classes of hydrochlorination reactions discussed in this review.
Figure 1: Mayr’s nucleophilicity parameters for several alkenes. References for each compound can be consulte...
Figure 2: Hydride affinities relating to the reactivity of the corresponding alkene towards hydrochlorination....
Scheme 2: Distinction of polar hydrochlorination reactions.
Scheme 3: Reactions of styrenes with HCl gas or HCl solutions.
Figure 3: Normal temperature dependence for the hydrochlorination of (Z)-but-2-ene.
Figure 4: Pentane slows down the hydrochlorination of 11.
Scheme 4: Recently reported hydrochlorinations of styrenes with HCl gas or HCl solutions.
Scheme 5: Hydrochlorination reactions with di- and trisubstituted alkenes.
Scheme 6: Hydrochlorination of fatty acids with liquified HCl.
Scheme 7: Hydrochlorination with HCl/DMPU solutions.
Scheme 8: Hydrochlorination with HCl generated from EtOH and AcCl.
Scheme 9: Hydrochlorination with HCl generated from H2O and TMSCl.
Scheme 10: Regioisomeric mixtures of chlorooctanes as a result of hydride shifts.
Scheme 11: Regioisomeric mixtures of products as a result of methyl shifts.
Scheme 12: Applications of the Kropp procedure on a preparative scale.
Scheme 13: Curious example of polar anti-Markovnikov hydrochlorination.
Scheme 14: Unexpected and expected hydrochlorinations with AlCl3.
Figure 5: Ex situ-generated HCl gas and in situ application for the hydrochlorination of activated alkenes (*...
Scheme 15: HCl generated by Grob fragmentation of 92.
Scheme 16: Formation of chlorophosphonium complex 104 and the reaction thereof with H2O.
Scheme 17: Snyder’s hydrochlorination with stoichiometric amounts of complex 104 or 108.
Scheme 18: In situ generation of HCl by mixing of MsOH with CaCl2.
Scheme 19: First hydrochlorination of alkenes using hydrochloric acid.
Scheme 20: Visible-light-promoted hydrochlorination.
Scheme 21: Silica gel-promoted hydrochlorination of alkenes with hydrochloric acid.
Scheme 22: Hydrochlorination with hydrochloric acid promoted by acetic acid or iron trichloride.
Figure 6: Metal hydride hydrogen atom transfer reactions vs cationic reactions; BDE (bond-dissociation energy...
Scheme 23: Carreira’s first report on radical hydrochlorinations of alkenes.
Figure 7: Mechanism for the cobalt hydride hydrogen atom transfer reaction reported by Carreira.
Scheme 24: Radical “hydrogenation” of alkenes; competing chlorination reactions.
Scheme 25: Bogers iron-catalyzed radical hydrochlorination.
Scheme 26: Hydrochlorination instead of hydrogenation product.
Scheme 27: Optimization of the Boger protocol by researchers from Merck [88,89].
Figure 8: Proposed mechanism for anti-Markovnikov hydrochlorination by Nicewicz.
Scheme 28: anti-Markovnikov hydrochlorinations as reported by Nicewicz.
Figure 9: Mechanism for anti-Markovnikov hydrochlorination according to Ritter.
Scheme 29: anti-Markovnikov hydrochlorinations as reported by Nicewicz; rr (regioisomeric ratio) corresponds t...
Scheme 30: anti-Markovnikov hydrochlorinations as reported by Liu.
Beilstein J. Org. Chem. 2024, 20, 661–671, doi:10.3762/bjoc.20.59
Graphical Abstract
Scheme 1: Background (a and b) and proposed carboamination MCR with diazo esters (c). a) Selected bioactive γ...
Scheme 2: Substrate scope of diazo compounds, 1,3-dienes and amines. aReactions (1/2/3/Pd(OAc)2/Xantphos = 0....
Scheme 3: Substrate scope of diazo compounds, allenes and amines. aReactions (1/5/3/Pd(OAc)2/Xantphos = 0.3.0...
Scheme 4: Mechanistic experiments. a) Radical trapping experiments with TEMPO. b) Exclusion of possible inter...
Scheme 5: Proposed mechanisms for the carboamination of 1,3-dienes or allenes with diazo esters and amines.
Scheme 6: Scale-up reactions and synthetic transformations. Reaction conditions: a) LiAlH4, THF, 0 °C; b) MeM...
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.
Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35
Graphical Abstract
Scheme 1: Comparison between Barton and NHPI ester radical precursors.
Scheme 2: Overview of the mechanisms and activation modes involved in radical generation from RAEs.
Scheme 3: Common mechanisms in photocatalysis.
Scheme 4: A) Giese-type radical addition of NHPI esters mediated by a reductive quenching photocatalytic cycl...
Scheme 5: A) Minisci-type radical addition of NHPI esters. B) Reaction mechanism involving an “off-cycle” red...
Scheme 6: Activation of NHPI esters through hydrogen-bonding in an oxidative quenching photocatalytic cycle.
Scheme 7: SET activation of RAE facilitated by a Lewis acid catalyst.
Scheme 8: PCET activation of NHPI esters in the context of a radical-redox annulation.
Scheme 9: Activation enabled by a strong excited-state reductant catalyst and its application in the dearomat...
Scheme 10: Proposed formation of an intramolecular charge-transfer complex in the synthesis of (spiro)anellate...
Scheme 11: Formation of a charge-transfer complex between enamides and NHPI esters enabled by a chiral phospha...
Scheme 12: Activation of NHPI ester through the formation of photoactive EDA-complexes.
Scheme 13: A) EDA complex-mediated radical hydroalkylation reactions of NHPI esters. B) Proposed mechanism for...
Scheme 14: Proposed radical chain mechanism initiated by EDA-complex formation.
Scheme 15: A) Photoinduced decarboxylative borylation. B) Proposed radical chain mechanism.
Scheme 16: A) Activation of NHPI esters mediated by PPh3/NaI. B) Proposed catalytic cycle involving EDA-comple...
Scheme 17: A) Radical generation facilitated by EDA complex formation between PTH1 catalyst and NHPI esters. B...
Scheme 18: Proposed catalytic cycle for the difunctionalization of styrenes.
Scheme 19: Formation of a charge-transfer complex between NHPI esters and Cs2CO3 enables decarboxylative amina...
Scheme 20: 3-Acetoxyquinuclidine as catalytic donor in the activation of TCNHPI esters.
Scheme 21: A) Photoinduced Cu-catalyzed decarboxylative amination. B) Proposed catalytic cycle. C) Radical clo...
Scheme 22: A) Photoinduced Pd-catalyzed aminoalkylation of 1,4-dienes. B) Proposed catalytic cycle.
Scheme 23: A) TM-catalyzed decarboxylative coupling of NHPI esters and organometallic reagents. B) Representat...
Scheme 24: Synthetic applications of the TM-catalyzed decarboxylative coupling of NHPI esters and organometall...
Scheme 25: A) Ni-catalyzed cross-electrophile coupling of NHPI esters. B) Representative catalytic cycle.
Scheme 26: A) Synthetic applications of decarboxylative cross-electrophile couplings. B) Decarboxylative aryla...
Scheme 27: A) Activation of tetrachlorophthalimide redox-active esters enabled by a low-valency Bi complex. B)...
Scheme 28: Activation of NHPI esters mediated by Zn0 applied in a Z-selective alkenylation reaction.
Scheme 29: A) Activation of NHPI esters enabled by a pyridine-boryl radical species applied to the decarboxyla...
Scheme 30: A) Decarboxylative coupling of RAE and aldehydes enabled by NHC-catalyzed radical relay. B) Propose...
Scheme 31: A) Decarboxylative C(sp3)–heteroatom coupling reaction of NHPI esters under NHC catalysis B) The NH...
Scheme 32: A) Electrochemical Giese-type radical addition of NHPI esters. B) Reaction mechanism.
Scheme 33: Electrochemical Minisci-type radical addition of NHPI-esters.
Scheme 34: Ni-electrocatalytic cross-electrophile coupling of NHPI esters with aryl iodides.
Scheme 35: A) Decarboxylative arylation of NHPI esters under Ag-Ni electrocatalysis B) Formation of AgNP on th...
Scheme 36: Synthetic applications of decarboxylative couplings of NHPI esters under Ni-electrocatalysis.
Scheme 37: Examples of natural product syntheses in which RAEs were used in key C–C bond forming reactions.
Beilstein J. Org. Chem. 2024, 20, 257–263, doi:10.3762/bjoc.20.26
Graphical Abstract
Scheme 1: Synthetic application of thianthrenium salts.
Scheme 2: Substrate scope. Reaction conditions: alkylthianthrenium salts 1 (0.3 mmol), thiophenols 2 (0.2 mmo...
Scheme 3: Substrate scope of amines. Reaction conditions: alkylthianthrenium salts 1 (0.3 mmol), amines 2 (0....
Scheme 4: Scale-up reaction.
Beilstein J. Org. Chem. 2024, 20, 155–161, doi:10.3762/bjoc.20.14
Graphical Abstract
Scheme 1: Methods for the C5-selective bromination of 8-aminoquinoline amides.
Scheme 2: Substrate scope of the 8-aminoquinoline amides. Reaction conditions: 1 (0.2 mmol), 2a (0.8 mmol), C...
Scheme 3: Substrate scope of the bromoalkanes. Reaction conditions: 1a (0.2 mmol), 2 (0.8 mmol), Cu(OAc)2·H2O...
Scheme 4: Further substrate scope investigations and gram-scale application.
Scheme 5: Control experiments and proposed mechanism.
Beilstein J. Org. Chem. 2023, 19, 1947–1956, doi:10.3762/bjoc.19.145
Graphical Abstract
Figure 1: Various types of stable singlet carbenes and their acronyms.
Figure 2: Various types of NHC·CS2 zwitterions and their coordination modes.
Scheme 1: Synthesis of CAAC·CS2 zwitterion 2 from its free carbene parent 1.
Scheme 2: Synthesis of CAAC·CS2 zwitterions 4a–c with KN(SiMe3)2.
Scheme 3: Synthesis of 1,2,3-triazolium iodides 5a–f.
Scheme 4: Synthesis of MIC·CS2 zwitterions 6a and 6b with KN(SiMe3)2.
Scheme 5: Synthesis of MIC·CS2 zwitterions 6c–f with NaOt-Bu.
Figure 3: ORTEP representations of zwitterions 4a (CAAC-Mes-Cy·CS2, top) and 4c (CAAC-Die-MePh·CS2, bottom) w...
Figure 4: ORTEP representations of zwitterions 6b (MIC-Dip-Ph-Me·CS2, top) and 6e (MIC-Mes-Bu-Me·CS2, bottom)...
Beilstein J. Org. Chem. 2023, 19, 1923–1932, doi:10.3762/bjoc.19.143
Graphical Abstract
Scheme 1: Representative [4 + 3] cycloaddition reactions of MBH carbonates derived from isatins.
Scheme 2: Synthesis of spiro[indoline-3,5'-[1,2]diazepines] 3a–m. Conditions: α-halogenated acylhydrazone (0....
Scheme 3: Synthesis of spiro[indoline-3,5'-[1,2]diazepines] 5a–g. Conditions: α-halogenated acylhydrazone (0....
Scheme 4: Synthesis of dihydrospiro[indoline-3,5'-[1,2]diazepines] 7a–n. Conditions: α-halogenated N-tosylhyd...
Figure 1: Single crystal structure of the spiro compound 7a.
Scheme 5: Proposed reaction mechanism.
Scheme 6: Gram-scale synthesis of compound 7c.
Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142
Graphical Abstract
Figure 1: (a, b) Schematics of previous approaches to dehalogenation-based reactions using molecular reductan...
Scheme 1: Selective deiodination of 2-iodobenzyl chloride.
Scheme 2: Reaction mechanisms for the reactions of dimeric reductants (D2) such as (Y-DMBI)2 derivatives with...
Figure 2: (a) A representative temporal evolution of % conversion (blue squares), % toluene yield (red diamon...
Figure 3: Top: UV–vis absorption spectra for the two dimeric reductants in THF emphasizing (a) the different ...
Figure 4: Transient absorption spectra of (a) (N-DMBI)2 in MeCN, (b) (N-DMBI)2 in toluene, and (c) (Cyc-DMBI)2...
Beilstein J. Org. Chem. 2023, 19, 1858–1866, doi:10.3762/bjoc.19.138
Graphical Abstract
Scheme 1: Reaction of the La@C2v-C82 anion with benzyl bromide derivatives.
Figure 1: Changes in absorption spectra during the reaction of La@C2v-C82 anion with 1a.
Figure 2: HPLC profiles of the reaction mixture. Conditions: Buckyprep column (⌀ = 4.6 × 250 mm); eluent, tol...
Figure 3: HPLC profiles (Buckyprep column (⌀ = 4.6 × 250 mm); eluent, toluene; flow rate, 1.0 mL/min; UV dete...
Figure 4: Absorption spectra of 2, 3, 4, and 5 in CS2 and absorption spectra of C14, C10, C18, and C9 in Ce@C2...
Figure 5: ORTEP drawing of 3a with thermal ellipsoids shown at 50% probability level. Only an independent uni...
Figure 6: (a) Charge density of La@C2v-C82 anion as a function of its POAV values and (b) an enlarged part vi...
Beilstein J. Org. Chem. 2023, 19, 1841–1848, doi:10.3762/bjoc.19.136
Graphical Abstract
Figure 1: Glutarimide-based immunomodulatory drugs (IMiDs) and CRBN ligands.
Scheme 1: Main literature approaches towards α-hetaryl glutarimides 1 (routes A and B) and new “diazo” method...
Scheme 2: Preparation of diazo reagent 5.
Scheme 3: Scope of NH insertion reaction of N-Boc-α-diazo glutarimide and various N-heterocycles. aIsolated y...
Figure 2: Examples of α-carbonyl NH-heterocycles for which N–H insertion products could not be obtained.
Scheme 4: Examples of N-deprotection of α-modified glutarimides 1.
Scheme 5: Preparation of NH2-containing derivative 10 via reduction of 6n.
Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120
Graphical Abstract
Figure 1: Porphyrin and crown ether.
Figure 2: Timeline demonstrating the contributions into the crown ether–porphyrin chemistry.
Figure 3: Tetra-crowned porphyrin 1 and dimer 2 formed upon K+ binding.
Figure 4: meso-Crowned 25-oxasmaragdyrins 3a–c and their boron(III) complexes (3a–c)-BF2.
Scheme 1: CsF ion-pair binding of 4. The molecular structure of 4-CsF is shown on the right [101].
Figure 5: CsF ion pair binding by 5. The molecular structure of 5-CsF is shown on the right [102].
Scheme 2: Ion-pair binding by 6. The molecular structure of (6-CsCl)2 is shown on the right [103].
Scheme 3: Hydrated fluoride binding by 7 [104].
Figure 6: β-Crowned porphyrin 8.
Figure 7: Crown ether-capped porphyrins 9.
Figure 8: The capped porphyrin 10 and complex [10-PQ](PF6)2.
Figure 9: The double-capped porphyrin 11.
Figure 10: Selected examples of iminoporphyrinoids [58,122].
Scheme 4: The synthesis of 13.
Scheme 5: Tripyrrane-based crown ether-embedding porphyrinoid 15.
Figure 11: Macrocycles 16–19 and their coordination compounds.
Scheme 6: The flexibility of 16-Co [66].
Figure 12: Hexagonal wheel composed of six 16-Co(III) monomers [66].
Scheme 7: The synthesis of 16-V [67].
Figure 13: The molecular structure of dimers [16-Mn]2 [67].
Scheme 8: Synthesis of crownphyrins 28–33. Compounds 23a/b and 29a/b were obtained from 4,7,10-trioxa-1,13-tr...
Figure 14: The molecular structures of 22a, 34a·(HCl)2, and 29b [69].
Figure 15: Molecular structures of 22a-Pb and (29b)2-Zn [69].
Scheme 9: Reactivity of 29a/b.
Scheme 10: Synthesis of 36 and 37 [131].
Scheme 11: Synthesis of 40–45.
Figure 16: Potential applications of porphyrin-crown ether hybrids.
Beilstein J. Org. Chem. 2023, 19, 1615–1619, doi:10.3762/bjoc.19.118
Graphical Abstract
Scheme 1: Synthesis of diverse azapolycycles from iron complex 2 derived from tricarbonyl(tropone)iron.
Figure 1: Complex alkaloids containing the 7-azabicyclo[4.3.1]decane ring system.
Scheme 2: Synthesis of Heck substrates. a) Substrate 7, reagents and conditions: 1) neat (5 equiv 5), 24 h; 2...
Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116
Graphical Abstract
Scheme 1: Oxidation of catechol and subsequent cross-linking. Scheme 1 redrawn from [3].
Scheme 2: (A) Structure of typical urushiol in Chinese lacquer, and (B) schematic process of laccase-catalyze...
Scheme 3: A) Primary amino acid sequence of mfp-1, mfp-3, and mfp-5 (Y: DOPA, K: lysine). B) Scheme showing e...
Scheme 4: Activation–deactivation equilibrium in nitroxide-mediated polymerizations. Bicomponent initiating s...
Scheme 5: Mechanism of a transition metal complex-mediated ATRP. Scheme 5 redrawn from [14].
Scheme 6: Mechanism of RAFT polymerization. Scheme 6 redrawn from [68].
Scheme 7: Degenerative transfer (a) and reversible termination (b) mechanism of OMRP. Scheme 7 redrawn from [70].
Scheme 8: Simplified mechanism of a RITP. Scheme 8 redrawn from [21].
Scheme 9: (A) Structures of π-conjugated conductive polymers. (B) Examples of conductive polymer synthesis vi...
Scheme 10: Possible regiochemical couplings in PATs. Scheme 10 redrawn from [79].
Scheme 11: General thiol-ene photopolymerization process. Scheme 11 redrawn from [81].
Scheme 12: (a) Three generations of Grubbs catalysts. (b) Proposed mechanism for photo-ROMP via a reductive qu...
Scheme 13: Pyrylium and thiopyrylium salts studied by Boydston et al. Scheme 13 redrawn from [91].
Scheme 14: A general illustration of post-polymerization modification by thiol–ene chemistry.
Scheme 15: Introduction of functionalities by nitroxide radical coupling of HO-TEMPO derivatives.
Scheme 16: Chemical reaction process scheme of DCP-induced crosslinking of LDPE. Scheme 16 redrawn from [126].
Scheme 17: A probable mechanism of radical-induced hydrosilylation.
Scheme 18: Polymer surface modification by homolytic dediazonation of diazonium salts.
Scheme 19: Photoinduced polymer surface modification or surface grafting using benzophenone.
Scheme 20: Depolymerization mechanism of common photoresists. (a) A possible mechanism of radiation decomposit...
Scheme 21: Proposed mechanisms of photooxidative depolymerization of polystyrene. (a) Scheme 21a was reprinted with perm...
Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106
Graphical Abstract
Scheme 1: Sulfur-containing bioactive molecules.
Scheme 2: Scandium-catalyzed synthesis of thiosulfonates.
Scheme 3: Palladium-catalyzed aryl(alkyl)thiolation of unactivated arenes.
Scheme 4: Catalytic cycle for Pd-catalyzed aryl(alkyl)thiolation of unactivated arenes.
Scheme 5: Iron- or boron-catalyzed C–H arylthiation of substituted phenols.
Scheme 6: Iron-catalyzed azidoalkylthiation of alkenes.
Scheme 7: Plausible mechanism for iron-catalyzed azidoalkylthiation of alkenes.
Scheme 8: BF3·Et2O‑mediated electrophilic cyclization of aryl alkynoates.
Scheme 9: Tentative mechanism for BF3·Et2O‑mediated electrophilic cyclization of aryl alkynoates.
Scheme 10: Construction of 6-substituted benzo[b]thiophenes.
Scheme 11: Plausible mechanism for construction of 6-substituted benzo[b]thiophenes.
Scheme 12: AlCl3‑catalyzed cyclization of N‑arylpropynamides with N‑sulfanylsuccinimides.
Scheme 13: Synthetic utility of AlCl3‑catalyzed cyclization of N‑arylpropynamides with N‑sulfanylsuccinimides.
Scheme 14: Sulfenoamination of alkenes with sulfonamides and N-sulfanylsuccinimides.
Scheme 15: Lewis acid/Brønsted acid controlled Pd-catalyzed functionalization of aryl C(sp2)–H bonds.
Scheme 16: Possible mechanism for Lewis acid/Brønsted acid controlled Pd-catalyzed functionalization of aryl C...
Scheme 17: FeCl3-catalyzed carbosulfenylation of unactivated alkenes.
Scheme 18: Copper-catalyzed electrophilic thiolation of organozinc halides.
Scheme 19: h-BN@Copper(II) nanomaterial catalyzed cross-coupling reaction of sulfoximines and N‑(arylthio)succ...
Scheme 20: AlCl3‑mediated cyclization and sulfenylation of 2‑alkyn-1-one O‑methyloximes.
Scheme 21: Lewis acid-promoted 2-substituted cyclopropane 1,1-dicarboxylates with sulfonamides and N-(arylthio...
Scheme 22: Lewis acid-mediated cyclization of β,γ-unsaturated oximes and hydrazones with N-(arylthio/seleno)su...
Scheme 23: Credible pathway for Lewis acid-mediated cyclization of β,γ-unsaturated oximes with N-(arylthio)suc...
Scheme 24: Synthesis of 4-chalcogenyl pyrazoles via chalcogenation/cyclization of α,β-alkynic hydrazones.
Scheme 25: Controllable synthesis of 3-thiolated pyrroles and pyrrolines.
Scheme 26: Possible mechanism for controllable synthesis of 3-thiolated pyrroles and pyrrolines.
Scheme 27: Co-catalyzed C2-sulfenylation and C2,C3-disulfenylation of indole derivatives.
Scheme 28: Plausible catalytic cycle for Co-catalyzed C2-sulfenylation and C2,C3-disulfenylation of indoles.
Scheme 29: C–H thioarylation of electron-rich arenes by iron(III) triflimide catalysis.
Scheme 30: Difunctionalization of alkynyl bromides with thiosulfonates and N-arylthio succinimides.·
Scheme 31: Suggested mechanism for difunctionalization of alkynyl bromides with thiosulfonates and N-arylthio ...
Scheme 32: Synthesis of thioesters, acyl disulfides, ketones, and amides by N-thiohydroxy succinimide esters.
Scheme 33: Proposed mechanism for metal-catalyzed selective acylation and acylthiolation.
Scheme 34: AlCl3-catalyzed synthesis of 3,4-bisthiolated pyrroles.
Scheme 35: α-Sulfenylation of aldehydes and ketones.
Scheme 36: Acid-catalyzed sulfetherification of unsaturated alcohols.
Scheme 37: Enantioselective sulfenylation of β-keto phosphonates.
Scheme 38: Organocatalyzed sulfenylation of 3‑substituted oxindoles.
Scheme 39: Sulfenylation and chlorination of β-ketoesters.
Scheme 40: Intramolecular sulfenoamination of olefins.
Scheme 41: Plausible mechanism for intramolecular sulfenoamination of olefins.
Scheme 42: α-Sulfenylation of 5H-oxazol-4-ones.
Scheme 43: Metal-free C–H sulfenylation of electron-rich arenes.
Scheme 44: TFA-promoted C–H sulfenylation indoles.
Scheme 45: Proposed mechanism for TFA-promoted C–H sulfenylation indoles.
Scheme 46: Organocatalyzed sulfenylation and selenenylation of 3-pyrrolyloxindoles.
Scheme 47: Organocatalyzed sulfenylation of S-based nucleophiles.
Scheme 48: Conjugate Lewis base Brønsted acid-catalyzed sulfenylation of N-heterocycles.
Scheme 49: Mechanism for activation of N-sulfanylsuccinimide by conjugate Lewis base Brønsted acid catalyst.
Scheme 50: Sulfenylation of deconjugated butyrolactams.
Scheme 51: Intramolecular sulfenofunctionalization of alkenes with phenols.
Scheme 52: Organocatalytic 1,3-difunctionalizations of Morita–Baylis–Hillman carbonates.
Scheme 53: Organocatalytic sulfenylation of β‑naphthols.
Scheme 54: Acid-promoted oxychalcogenation of o‑vinylanilides with N‑(arylthio/arylseleno)succinimides.
Scheme 55: Lewis base/Brønsted acid dual-catalytic C–H sulfenylation of aryls.
Scheme 56: Lewis base-catalyzed sulfenoamidation of alkenes.
Scheme 57: Cyclization of allylic amide using a Brønsted acid and tetrabutylammonium chloride.
Scheme 58: Catalytic electrophilic thiocarbocyclization of allenes with N-thiosuccinimides.
Scheme 59: Suggested mechanism for electrophilic thiocarbocyclization of allenes with N-thiosuccinimides.
Scheme 60: Chiral chalcogenide-catalyzed enantioselective hydrothiolation of alkenes.
Scheme 61: Proposed mechanism for chalcogenide-catalyzed enantioselective hydrothiolation of alkenes.
Scheme 62: Organocatalytic sulfenylation for synthesis a diheteroatom-bearing tetrasubstituted carbon centre.
Scheme 63: Thiolative cyclization of yne-ynamides.
Scheme 64: Synthesis of alkynyl and acyl disulfides from reaction of thiols with N-alkynylthio phthalimides.
Scheme 65: Oxysulfenylation of alkenes with 1-(arylthio)pyrrolidine-2,5-diones and alcohols.
Scheme 66: Arylthiolation of arylamines with (arylthio)-pyrrolidine-2,5-diones.
Scheme 67: Catalyst-free isothiocyanatoalkylthiation of styrenes.
Scheme 68: Sulfenylation of (E)-β-chlorovinyl ketones toward 3,4-dimercaptofurans.
Scheme 69: HCl-promoted intermolecular 1, 2-thiofunctionalization of aromatic alkenes.
Scheme 70: Possible mechanism for HCl-promoted 1,2-thiofunctionalization of aromatic alkenes.
Scheme 71: Coupling reaction of diazo compounds with N-sulfenylsuccinimides.
Scheme 72: Multicomponent reactions of disulfides with isocyanides and other nucleophiles.
Scheme 73: α-Sulfenylation and β-sulfenylation of α,β-unsaturated carbonyl compounds.
Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102
Graphical Abstract
Scheme 1: In situ generation of imidazolylidene carbene.
Scheme 2: Hg(II) complex of NHC.
Scheme 3: Isolable and bottlable carbene reported by Arduengo [3].
Scheme 4: First air-stable carbene synthesized by Arduengo in 1992 [5].
Figure 1: General structure of an NHC.
Figure 2: Stabilization of an NHC by donation of the lone pair electrons into the vacant p-orbital (LUMO) at ...
Figure 3: Abnormal NHC reported by Bertrand [8,9].
Figure 4: Cu(d) orbital to σ*C-N(NHC) interactions in NHC–CuX complexes computed at the B3LYP/def2-SVP level ...
Figure 5: Molecular orbital contributions to the NHC–metal bond.
Scheme 5: Synthesis of NHC–Cu(I) complexes by deprotonation of NHC precursors with a base.
Scheme 6: Synthesis of [NHC–CuX] complexes.
Scheme 7: Synthesis of [(ICy)CuX] and [(It-Bu)CuX] complexes.
Scheme 8: Synthesis of iodido-bridged copper–NHC complexes by deprotonation of benzimidazolium salts reported...
Scheme 9: Synthesis of copper complexes by deprotonation of triazolium salts.
Scheme 10: Synthesis of thiazolylidene–Cu(I) complex by deprotonation with KOt-Bu.
Scheme 11: Preparation of NHC–Cu(I) complexes.
Scheme 12: Synthesis of methylmalonic acid-derived anionic [(26a,b)CuCl]Li(THF)2 and zwitterionic (28) heterol...
Scheme 13: Synthesis of diaminocarbene and diamidocarbene (DAC)–Cu(I) complexes.
Scheme 14: Synthesis of the cationic (NHC)2Cu(I) complex 39 from benzimidazolium salts 38 with tetrakis(aceton...
Scheme 15: Synthesis of NHC and ADC (acyclic diamino carbenes) Cu(I) hexamethyldisilazide complexes reported b...
Scheme 16: Synthesis of NHC–copper(I) complexes using an acetylacetonate-functionalized imidazolium zwitterion...
Scheme 17: Synthesis of NHC–Cu(I) complexes through deprotonation of azolium salts with Cu2O.
Scheme 18: Synthesis of NHC–CuBr complex through deprotonation with Cu2O reported by Kolychev [31].
Scheme 19: Synthesis of chiral NHC–CuBr complexes from phenoxyimine-imidazolium salts reported by Douthwaite a...
Scheme 20: Preparation of linear neutral NHC–CuCl complexes through the use of Cu2O. For abbreviations, please...
Scheme 21: Synthesis of abnormal-NHC–copper(I) complexes by Bertrand, Cazin and co-workers [35].
Scheme 22: Microwave-assisted synthesis of thiazolylidene/benzothiazolylidene–CuBr complexes by Bansal and co-...
Scheme 23: Synthesis of NHC–CuX complexes through transmetallation.
Scheme 24: Preparation of six- or seven-membered NHC–Cu(I) complexes through transmetalation from Ag(I) comple...
Scheme 25: Synthesis of 1,2,3-triazolylidene–CuCl complexes through transmetallation of Ag(I) complexes genera...
Scheme 26: Synthesis of NHC–copper complexes having both Cu(I) and Cu(II) units through transmetalation report...
Scheme 27: Synthesis of new [(IPr(CH2)3Si(OiPr)3)CuX] complexes and anchoring on MCM-41.
Scheme 28: Synthesis of bis(trimethylsilyl)phosphide–Cu(I)–NHC complexes through ligand displacement.
Scheme 29: Synthesis of silyl- and stannyl [(NHC)Cu−ER3] complexes.
Scheme 30: Synthesis of amido-, phenolato-, thiophenolato–Cu(NHC) complexes.
Scheme 31: Synthesis of first isolable NHC–Cu–difluoromethyl complexes reported by Sanford et al. [44].
Scheme 32: Synthesis of NHC–Cu(I)–bifluoride complexes reported by Riant, Leyssens and co-workers [45].
Scheme 33: Conjugate addition of Et2Zn to enones catalyzed by an NHC–Cu(I) complex reported by Woodward in 200...
Scheme 34: Hydrosilylation of a carbonyl group.
Scheme 35: NHC–Cu(I)-catalyzed hydrosilylation of ketones reported by Nolan et al. [48,49].
Scheme 36: Application of chiral NHC–CuCl complex 104 for the enantioselective hydrosilylation of ketones.
Scheme 37: Hydrosilylation reactions catalyzed by NHC–Cu(Ot-Bu) complexes.
Scheme 38: NHC–CuCl catalyzed carbonylative silylation of alkyl halides.
Scheme 39: Nucleophilic conjugate addition to an activated C=C bond.
Figure 6: Molecular electrostatic potential maps (MESP) of two NHC–CuX complexes computed at the B3LYP/def2-S...
Scheme 40: Conjugate addition of Grignard reagents to 3-alkyl-substituted cyclohexenones catalyzed by a chiral...
Scheme 41: NHC–copper complex-catalyzed conjugate addition of Grignard reagent to 3-substituted hexenone repor...
Scheme 42: Conjugate addition or organoaluminum reagents to β-substituted cyclic enones.
Scheme 43: Conjugate addition of boronates to acyclic α,β-unsaturated carboxylic esters, ketones, and thioeste...
Scheme 44: NHC–Cu(I)-catalyzed hydroboration of an allene reported by Hoveyda [63].
Scheme 45: Conjugate addition of Et2Zn to cyclohexenone catalyzed by NHC–Cu(I) complex derived from benzimidaz...
Scheme 46: Asymmetric conjugate addition of diethylzinc to 3-nonen-2-one catalyzed by NHC–Cu complexes derived...
Scheme 47: General scheme of a [3 + 2] cycloaddition reaction.
Scheme 48: [3 + 2] Cycloaddition of azides with alkynes catalyzed by NHC–Cu(I) complexes reported by Diez-Gonz...
Scheme 49: Application of NHC–CuCl/N-donor combination to catalyze the [3 + 2] cycloaddition of benzyl azide w...
Scheme 50: [3 + 2] Cycloaddition of azides with acetylenes catalyzed by bis(NHC)–Cu complex 131 and mixed NHC–...
Figure 7: NHC–CuCl complex 133 as catalyst for the [3 + 2] cycloaddition of alkynes with azides at room tempe...
Scheme 51: [3 + 2] Cycloaddition of a bulky azide with an alkynylpyridine using [(NHC)Cu(μ-I)2Cu(NHC)] copper ...
Scheme 52: [3 + 2] Cycloaddition of benzyl azide with phenylacetylene under homogeneous and heterogeneous cata...
Scheme 53: [3 + 2] Cycloaddition of benzyl azide with acetylenes catalyzed by bisthiazolylidene dicopper(I) co...
Figure 8: Copper (I)–NHC linear coordination polymer 137 and its conversion into tetranuclear (138) and dinuc...
Scheme 54: An A3 reaction.
Scheme 55: Synthesis of SiO2-immobilized NHC–Cu(I) catalyst 141 and its application in the A3-coupling reactio...
Scheme 56: Preparation of dual-purpose Ru@SiO2–[(NHC)CuCl] catalyst system 142 developed by Bordet, Leitner an...
Scheme 57: Application of the catalyst system Ru@SiO2–[Cu(NHC)] 142 to the one-pot tandem A3 reaction and hydr...
Scheme 58: A3 reaction of phenylacetylene with secondary amines and aldehydes catalyzed by benzothiazolylidene...
Figure 9: Kohn–Sham HOMOs of phenylacetylene and NHC–Cu(I)–phenylacetylene complex computed at the B3LYP/def2...
Figure 10: Energies of the FMOs of phenylacetylene, iminium ion, and NHC–Cu(I)–phenylacetylene complex compute...
Scheme 59: NHC–Cu(I) catalyzed diboration of ketones 147 by reacting with bis(pinacolato)diboron (148) reporte...
Scheme 60: Protoboration of terminal allenes catalyzed by NHC–Cu(I) complexes reported by Hoveyda and co-worke...
Scheme 61: NHC–CuCl-catalyzed borylation of α-alkoxyallenes to give 2-boryl-1,3-butadienes.
Scheme 62: Regioselective hydroborylation of propargylic alcohols and ethers catalyzed by NHC–CuCl complexes 1...
Scheme 63: NHC–CuOt-Bu-catalyzed semihydrogenation and hydroborylation of alkynes.
Scheme 64: Enantioselective NHC–Cu(I)-catalyzed hydroborations of 1,1-disubstituted aryl olefins reported by H...
Scheme 65: Enantioselective NHC–Cu(I)-catalyzed hydroboration of exocyclic 1,1-disubstituted alkenes reported ...
Scheme 66: Markovnikov-selective NHC–CuOH-catalyzed hydroboration of alkenes and alkynes reported by Jones et ...
Scheme 67: Dehydrogenative borylation and silylation of styrenes catalyzed by NHC–CuOt-Bu complexes developed ...
Scheme 68: N–H/C(sp2)–H carboxylation catalyzed by NHC–CuOH complexes.
Scheme 69: C–H Carboxylation of benzoxazole and benzothiazole derivatives with CO2 using a 1,2,3-triazol-5-yli...
Scheme 70: Use of Cu(I) complex derived from diethylene glycol-functionalized imidazo[1,5,a] pyridin-3-ylidene...
Scheme 71: Allylation and alkenylation of polyfluoroarenes and heteroarenes catalyzed by NHC–Cu(I) complexes r...
Scheme 72: Enantioselective C(sp2)–H allylation of (benz)oxazoles and benzothiazoles with γ,γ-disubstituted pr...
Scheme 73: C(sp2)–H arylation of arenes catalyzed by dual NHC–Cu/NHC–Pd catalytic system.
Scheme 74: C(sp2)–H Amidation of (hetero)arenes with N-chlorocarbamates/N-chloro-N-sodiocarbamates catalyzed b...
Scheme 75: NHC–CuI catalyzed thiolation of benzothiazoles and benzoxazoles.
Beilstein J. Org. Chem. 2023, 19, 1225–1233, doi:10.3762/bjoc.19.90
Graphical Abstract
Scheme 1: Overview of the RLT mechanism in nature and in literature. I: The radical rebound mechanism in cyto...
Scheme 2: Areas of recent work on RLT development and application in catalysis. I: Reported RLT pathways ofte...
Scheme 3: The incorporation of RLT catalysis in ATRA photocatalysis. I: The reported method is compatible wit...
Scheme 4: Pioneering and recent work on decarboxylative functionalization involving a posited RLT pathway. I:...
Scheme 5: Our lab reported decarboxylative azidation of aliphatic and benzylic acids. I: The reaction proceed...
Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86
Graphical Abstract
Figure 1: Generic representation of halogen bonding.
Figure 2: Quantitative evaluation of σ-holes in monovalent iodine-containing compounds; and, qualitative mole...
Figure 3: Quantitative evaluation of σ-holes in hypervalent iodine-containing molecules; and, qualitative MEP...
Figure 4: Quantitative evaluation of σ-holes in iodonium ylides; and, qualitative MEP map of I-12 from −0.083...
Scheme 1: Outline of possible reaction pathways between iodonium ylides and Lewis basic nucleophiles (top); a...
Scheme 2: Metal-free cyclopropanations of iodonium ylides, either as intermolecular (a) or intramolecular pro...
Figure 5: Zwitterionic mechanism for intramolecular cyclopropanation of iodonium ylides (left); and, stepwise...
Scheme 3: Metal-free intramolecular cyclopropanation of iodonium ylides.
Figure 6: Concerted cycloaddition pathway for the metal-free, intramolecular cyclopropanation of iodonium yli...
Scheme 4: Reaction of ylide 6 with diphenylketene to form lactone 24 and 25.
Figure 7: Nucleophilic (top) and electrophilic (bottom) addition pathways proposed by Koser and Hadjiarapoglo...
Scheme 5: Indoline synthesis from acyclic iodonium ylide 31 and tertiary amines.
Scheme 6: N-Heterocycle synthesis from acyclic iodonium ylide 31 and secondary amines.
Figure 8: Proposed mechanism for the formation of 33a from iodonium ylides and amines, involving an initial h...
Scheme 7: Indoline synthesis from acyclic iodonium ylides 39 and tertiary amines under blue light photocataly...
Scheme 8: Metal-free cycloproponation of iodonium ylides under blue LED irradiation. aUsing trans-β-methylsty...
Figure 9: Proposed mechanism of the cyclopropanation between iodonium ylides and alkenes under blue LED irrad...
Scheme 9: Formal C–H alkylation of iodonium ylides by nucleophilic heterocycles under blue LED irradiation.
Figure 10: Proposed mechanism of the formal C–H insertion of pyrrole under blue LED irradiation.
Scheme 10: X–H insertions between iodonium ylides and carboxylic acids, phenols and thiophenols.
Figure 11: Mechanistic proposal for the X–H insertion reactions of iodonium ylides.
Scheme 11: Radiofluorination of biphenyl using iodonium ylides 54a–e derived from various β-dicarbonyl auxilia...
Scheme 12: Radiofluorination of arenes using spirocycle-derived iodonium ylides 56.
Scheme 13: Radiofluorination of arenes using SPIAd-derived iodonium ylides 58.
Figure 12: Calculated reaction coordinate for the radiofluorination of iodonium ylide 60.
Scheme 14: Radiofluorination of iodonium ylides possessing various ortho- and para-substituents on the iodoare...
Figure 13: Difference in Gibbs activation energy for ortho- or para-anisyl derived iodonium ylides 63a and 63b....
Figure 14: Proposed equilibration of intermediates to transit between 64a (the initial adduct formed between 6...
Scheme 15: Comparison of 31 and ortho-methoxy iodonium ylide 39 in rhodium-catalyzed cyclopropanation and cycl...
Figure 15: X-ray crystal structure of dimeric 39 [6], (CCDC# 893474) [143,144].
Scheme 16: Enaminone synthesis using diazonium and iodonium ylides.
Figure 16: Transition state calculations for enaminone synthesis from iodonium ylides and thioamides.
Scheme 17: The reaction between ylides 73a–f and N-methylpyrrole under 365 nm UV irradiation.
Figure 17: Crystal structures of 76c (top) and 76e (bottom) [101], (CCDC# 2104180 & 2104181) [143,144].
Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81
Graphical Abstract
Figure 1: Oxidative and reductive activations of organic compounds harvesting photoredox catalysis.
Figure 2: General catalytic cycles of radical ion conPET (left) and radical ion e-PRC (right).
Figure 3: “Beginner’s guide”: comparison between advantages, capacities, and prospectives of conPET and PEC.
Figure 4: A) conPET reductive dehalogenation of aryl halides with PDI. B) Reductive C–H arylation with pyrrol...
Figure 5: A) Chromoselective mono- and disubstitution or polybrominated pyrimidines with pyrroles. B) Sequent...
Figure 6: A) Synthesis of pyrrolo[1,2-a]quinolines. B) Synthesis of ullazines.
Figure 7: A) Reductive phosphorylation of aryl halides via conPET. B) Selected examples from the substrate sc...
Figure 8: A) Reductive dehalogenation of aryl halides via conPET and selected examples from the substrate sco...
Figure 9: A) Reductive C–H arylation of aryl halides via conPET (top) and selected examples from the substrat...
Figure 10: A) Reductive hydrodehalogenation of aryl halides with Mes-Acr-BF4. B) Selected examples from the su...
Figure 11: A) Reductive hydrodechlorination of aryl chlorides with 4-DPAIPN. B) Proposed formation of CO2•−. C...
Figure 12: A) Reductive conPET borylation with 3CzEPAIPN (top) and selected examples from the substrate scope ...
Figure 13: Scale-up of conPET phosphorylation with 3CzEPAIPN.
Figure 14: A) Borylation of 1d. B) Characteristics and structure of PC1 with green and red parts showing the l...
Figure 15: A) Reductive C–H arylation scope with polysulfide conPET (top) and selected examples from the subst...
Figure 16: Scale-up of A) C–H arylation and B) dehaloborylation with polysulfide photocatalysis in continuous-...
Figure 17: A) Formation of [Ir1]0 and [Ir2]0 upon PET between [Ir1]+ and Et3N. B) Mechanism of multi-photon ta...
Figure 18: A) Reductive hydrodehalogenation of aryl halides via multi-photon tandem photocatalysis. B) Selecte...
Figure 19: A) Carbonylative amidation of aryl halides in continuous flow. B) Selected examples from the substr...
Figure 20: A) General scheme for reductive (RQ) and oxidative quenching (OQ) protocols using [FeIII(btz)3](PF6)...
Figure 21: A) Carbonylative amidation of alkyl iodides with [IrIII(ppy)2(dtbbpy)]PF6. B) Selected examples fro...
Figure 22: A) Carboxylative C–N bond cleavage in cyclic amines. B) Selected examples from the substrate scope....
Figure 23: A) Formal reduction of alkenes to alkanes via transfer hydrogenation. B) Selected examples from the...
Figure 24: A) Birch-type reduction of benzenes with PMP-BPI. B) Selected examples from the substrate scope (sc...
Figure 25: Proposed mechanism of the OH− mediated conPET Birch-type reduction of benzene via generation of sol...
Figure 26: Reductive detosylation of N-tosylated amides with Mes-Acr-BF4. B) Selected examples from the substr...
Figure 27: A) Reductive detosylation of N-tosyl amides by dual PRC. B) Selected examples from the substrate sc...
Figure 28: A) Mechanism of the dual PRC based on PET between [Cu(dap)2]+ and DCA. B) Mechanism of the dual PRC...
Figure 29: A) N–O bond cleavage in Weinreb amides with anthracene. B) N–O bond cleavage in Weinreb amides rely...
Figure 30: A) Pentafluorosulfanylation and fluoride elimination. B) Mechanism of the pentafluorosulfanylation ...
Figure 31: A) α-Alkoxypentafluorosulfanylation (top) and selected examples from the substrate scope (bottom). ...
Figure 32: A) Oxidative amination of arenes with azoles catalyzed by N-Ph PTZ. B) Selected examples from the s...
Figure 33: A) C(sp3)–H bond activation by HAT via chloride oxidation by *N-Ph PTZ•+. B) Proposed mechanism for...
Figure 34: A) Recycling e-PRC C–H azolation of electron-rich arenes with pyrazoles using Mes-Acr+ as a photoca...
Figure 35: A) Radical ion e-PRC direct oxidation of unactivated arenes using TAC+ as an electro-activated phot...
Figure 36: A) Radical ion e-PRC direct oxidation of unactivated arenes using TPA as an electro-activated photo...
Figure 37: Proposed mechanism (top) and mode of preassembly (bottom).
Figure 38: A) Possible preassemblies of reactive (left) vs unreactive (right) arenes. B) Calculated spin densi...
Figure 39: A) Recycling e-PRC C(sp2 )–H acetoxylation of arenes using DDQ as a photocatalyst. B) Proposed cata...
Figure 40: Gram scale hydroxylation of benzene in a recirculated flow setup.
Figure 41: A) Radical ion e-PRC vicinal diamination of alkylarenes using TAC+ as an electro-activated photocat...
Figure 42: A) Sequential oxygenation of multiple adjacent C–H bonds under radical ion e-PRC using TAC+ as an e...
Figure 43: A) Enantioselective recycling e-PRC cyanation of benzylic C–H bonds using ADQS as photocatalyst. B)...
Figure 44: Proposed tandem mechanism by Xu and co-workers.
Figure 45: A) Enantioselective recycling e-PRC decarboxylative cyanation using Cu(acac)2, Ce(OTf)3 and a box l...
Figure 46: A) Enantioselective recycling e-PRC benzylic cyanation using Cu(MeCN)4BF4, box ligand and anthraqui...
Figure 47: A) Radical ion e-PRC acetoxyhydroxylation of aryl olefins using TAC+ as an electro-activated photoc...
Figure 48: Selected examples from the substrate scope.
Figure 49: Photoelectrochemical acetoxyhydroxylation in a recirculated flow setup.
Figure 50: A) Radical ion e-PRC aminooxygenation of aryl olefins using TAC+ as an electro-activated photocatal...
Figure 51: A) Recycling e-PRC C–H alkylation of heteroarenes with organic trifluoroborates using Mes-Acr+ as p...
Figure 52: A) Recycling e-PRC decarboxylative C–H alkylation of heteroarenes using CeCl3·7H2O as catalyst. B) ...
Figure 53: A) Recycling e-PRC decarboxylative C–H alkylation of heteroarenes using Fe(NH4)2(SO4)2·6H2O as cata...
Figure 54: A) Recycling e-PRC C–H alkylation of heteroarenes with alkyl oxalates and 4CzIPN as photocatalyst. ...
Figure 55: A) Recycling e-PRC decarboxylative C–H carbamoylation of heteroarenes using 4CzIPN as photocatalyst...
Figure 56: A) Photoelectrochemical HAT-mediated hydrocarbon activation via the chlorine radical. B) Proposed m...
Figure 57: A) Selected examples from the substrate scope. B) Gram and decagram scale semi-continuous flow PEC ...
Figure 58: A) Photoelectrochemical HAT-mediated dehydrogenative coupling of benzothiazoles with aliphatic C–H ...
Figure 59: A) Photoelectrochemical HAT activation of ethers using electro-activated TAC+ as photocatalyst. B) ...
Figure 60: Selected examples from the substrate scope.
Figure 61: A) Photoelectrochemical HAT-mediated synthesis of alkylated benzimidazo-fused isoquinolinones using...
Figure 62: A) Decoupled photoelectrochemical cerium-catalyzed oxydichlorination of alkynes using CeCl3 as cata...
Figure 63: Proposed decoupled photoelectrochemical mechanism.
Figure 64: A) Decoupled photoelectrochemical ring-opening bromination of tertiary cycloalkanols using MgBr2 as...
Figure 65: A) Recycling e-PRC ring-opening functionalization of cycloalkanols using CeCl3 as catalyst. B) Prop...
Figure 66: Selected examples from the substrate scope of the PEC ring-opening functionalization.
Figure 67: A) Radical ion e-PRC reduction of chloro- and bromoarenes using DCA as catalyst and various accepto...
Figure 68: A) Screening of different phthalimide derivatives as catalyst for the e-PRC reduction of aryl halid...
Figure 69: Screening of different organic catalysts for the e-PRC reduction of trialkylanilium salts.
Figure 70: A) e-PRC reduction of phosphonated phenols and anilinium salts. B) Selected examples from the subst...
Figure 71: A) ConPET and e-PRC reduction of 4-bromobenzonitrile using a naphthalene diimide (NDI) precatalyst ...
Figure 72: A) Radical ion e-PRC reduction of phosphinated aliphatic alcohols with n-BuO-NpMI as catalyst. B) C...
Figure 73: Selected examples from the substrate scope.
Figure 74: A) Recycling e-PRC reductive dimerization of benzylic chlorides using a [Cu2] catalyst. B) Proposed...
Figure 75: A) Decoupled photoelectrochemical C–H alkylation of heteroarenes through deamination of Katritzky s...
Figure 76: Proposed mechanism by Chen and co-workers.
Beilstein J. Org. Chem. 2023, 19, 918–927, doi:10.3762/bjoc.19.70
Graphical Abstract
Figure 1: (a) Transformations of DMAT to different classes of ergot alkaloids. (b) and (c) Strategies for the...
Scheme 1: Synthesis of compound 5.
Scheme 2: Photoredox-catalyzed radical decarboxylative cyclization of 5.
Figure 2: Proposed reaction mechanism for photoredox-catalyzed radical decarboxylative cyclization.
Scheme 3: Synthesis of tryptophan derivatives 8 and 10.
Figure 3: Proposed reaction mechanism for photoredox-catalyzed radical decarboxylative cyclization.
Scheme 4: Methylation of 11 and the formal total synthesis of (±)-6,7-secoagroclavine.