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Search for "aryllithium reagents" in Full Text gives 5 result(s) in Beilstein Journal of Organic Chemistry.
Synthesis and applications of alkenyl chlorides (vinyl chlorides): a review
- Daniel S. Müller
Beilstein J. Org. Chem. 2026, 22, 1–63, doi:10.3762/bjoc.22.1
Graphical Abstract
Figure 1: Representative alkenyl chloride motifs in natural products. References: Pinnaic acid [8], haterumalide ...
Figure 2: Representative alkenyl chloride motifs in pharmaceuticals and pesticides. References: clomifene [25], e...
Figure 3: Graphical overview of previously published reviews addressing the synthesis of alkenyl chlorides.
Figure 4: Classification of synthetic approaches to alkenyl chlorides.
Scheme 1: Early works by Friedel, Henry, and Favorsky.
Scheme 2: Product distribution obtained by H NMR integration of crude compound as observed by Kagan and co-wo...
Scheme 3: Side reactions observed for the reaction of 14 with PCl5.
Scheme 4: Only compounds 15 and 18 were observed in the presence of Hünig’s base.
Scheme 5: Efficient synthesis of dichloride 15 at low temperatures.
Scheme 6: Various syntheses of alkenyl chlorides on larger scale.
Scheme 7: Scope of the reaction of ketones with PCl5 in boiling cyclohexane.
Scheme 8: Side reactions occur when using excess amounts of PCl5.
Scheme 9: Formation of versatile β-chlorovinyl ketones.
Scheme 10: Mixture of PCl5 and PCl3 used for the synthesis of 49.
Scheme 11: Catechol–PCl3 reagents for the synthesis of alkenyl chlorides.
Scheme 12: (PhO)3P–halogen-based reagents for the synthesis of alkenyl halides.
Scheme 13: Preparation of alkenyl chlorides from alkenyl phosphates.
Scheme 14: Preparation of alkenyl chlorides by treatment of ketones with the Vilsmeier reagent.
Scheme 15: Preparation of electron-rich alkenyl chlorides by treatment of ketones with the Vilsmeier reagent.
Scheme 16: Cu-promoted synthesis of alkenyl chlorides from ketones and POCl3.
Figure 5: GC yield of 9 depending on time and reaction temperature.
Figure 6: Broken reaction flask after attempts to clean the polymerized residue.
Figure 7: GC yield of 9 depending on the amount of CuCl and time.
Scheme 17: Treatment of 4-chromanones with PCl3.
Scheme 18: Synthesis of alkenyl chlorides from the reaction of ketones with acyl chlorides.
Scheme 19: ZnCl2-promoted alkenyl chloride synthesis.
Scheme 20: Regeneration of acid chlorides by triphosgene.
Scheme 21: Alkenyl chlorides from ketones and triphosgene.
Scheme 22: Various substitution reactions.
Scheme 23: Vinylic Finkelstein reactions reported by Evano and co-workers.
Scheme 24: Challenge of selective monohydrochlorination of alkynes.
Scheme 25: Sterically encumbered internal alkynes furnish the hydrochlorination products in high yield.
Scheme 26: Recent work by Kropp with HCl absorbed on alumina.
Scheme 27: High selectivities for monhydrochlorination with nitromethane/acetic acid as solvent.
Figure 8: Functionalized alkynes which typically afford the monhydrochlorinated products.
Scheme 28: Related chorosulfonylation and chloroamination reactions.
Scheme 29: Reaction of organometallic reagents with chlorine electrophiles.
Scheme 30: Elimination reactions of dichlorides to furnish alkenyl chlorides.
Scheme 31: Elimination reactions of allyl chloride 182 to furnish alkenyl chloride 183.
Scheme 32: Detailed studies by Schlosser on the elimination of dichloro compounds.
Scheme 33: Stereoselective variation caused by change of solvent.
Scheme 34: Elimination of gem-dichloride 189 to afford alkene 190.
Scheme 35: Oxidation of enones to dichlorides and in situ elimination thereof.
Scheme 36: Oxidation of allylic alcohols to dichlorides and in situ elimination thereof.
Scheme 37: Chlorination of styrenes with SOCl2 and elimination thereof.
Scheme 38: Chlorination of styrenes with SOCl2 and elimination thereof.
Scheme 39: Fluorine–chlorine exchange followed by elimination.
Scheme 40: Intercepting cations with alkynes and trapping of the alkenyl cation intermediate with chloride.
Scheme 41: Investigations by Mayr and co-workers.
Scheme 42: In situ activation of benzyl alcohol 230 with BCl3.
Scheme 43: In situ activation of benzylic alcohols with TiCl4.
Scheme 44: In situ activation of benzylic alcohols with FeCl3.
Scheme 45: In situ activation of benzylic alcohols with FeCl3.
Scheme 46: In situ activation of aliphatic chlorides and alcohols with ZnCl2, InCl3, and FeCl3.
Scheme 47: In situ generation of benzylic cations and trapping thereof with alkynes.
Scheme 48: Intramolecular trapping reactions affording alkenyl halides.
Scheme 49: Intramolecular trapping reactions affording alkenyl chlorides.
Scheme 50: Intramolecular trapping reactions of oxonium and iminium ions affording alkenyl chlorides.
Scheme 51: Palladium and nickel-catalyzed coupling reactions to afford alkenyl chlorides.
Scheme 52: Rhodium-catalyzed couplings of 1,2-trans-dichloroethene with arylboronic esters.
Scheme 53: First report on monoselective coupling reactions for 1,1-dichloroalkenes.
Scheme 54: Negishi’s and Barluenga’s contributions.
Scheme 55: First mechanistic investigation by Johnson and co-workers.
Scheme 56: First successful cross-metathesis with choroalkene 260.
Scheme 57: Subsequent studies by Johnson.
Scheme 58: Hoveyda and Schrock’s work on stereoretentive cross-metathesis with molybdenum-based catalysts.
Scheme 59: Related work with (Z)-dichloroethene.
Scheme 60: Further ligand refinement and traceless protection of functional groups with HBpin.
Scheme 61: Alkenyl chloride synthesis by Wittig reaction.
Scheme 62: Alkenyl chloride synthesis by Julia olefination.
Scheme 63: Alkenyl chloride synthesis by reaction of ketones with Mg/TiCl4 mixture.
Scheme 64: Frequently used allylic substitution reactions which lead to alkenyl chlorides.
Scheme 65: Enantioselective allylic substitutions.
Scheme 66: Synthesis of alkenyl chlorides bearing an electron-withdrawing group.
Scheme 67: Synthesis of α-nitroalkenyl chlorides from aldehydes.
Scheme 68: Synthesis of alkenyl chlorides via elimination of an in situ generated geminal dihalide.
Scheme 69: Carbenoid approach reported by Pace.
Scheme 70: Carbenoid approach reported by Pace.
Scheme 71: Ring opening of cyclopropenes in the presence of MgCl2.
Scheme 72: Electrophilic chlorination of alkenyl MIDA boronates to Z- or E-alkenyl chlorides.
Scheme 73: Hydroalumination and hydroboration of alkynyl chlorides.
Scheme 74: Carbolithiation of chloroalkynes.
Scheme 75: Chlorination of enamine 420.
Scheme 76: Alkyne synthesis by elimination of alkenyl chlorides.
Scheme 77: Reductive lithiation of akenyl chlorides.
Scheme 78: Reactions of alkenyl chlorides with organolithium reagents.
Scheme 79: Reactions of alkenyl chlorides with organolithium reagents.
Scheme 80: Addition–elimination reaction of alkenyl chloride 9 with organolithium reagents.
Scheme 81: C–H insertions of lithiumcarbenoids.
Scheme 82: Pd-catalyzed coupling reactions with alkenyl chlorides as coupling partner.
Scheme 83: Ni-catalyzed coupling of alkenylcopper reagent with alkenyl chloride 183.
Scheme 84: Ni-catalyzed coupling of heterocycle 472 with alkenyl chloride 473.
Scheme 85: Synthesis of α-chloroketones by oxidation of alkenyl chlorides.
Scheme 86: Tetrahalogenoferrate(III)-promoted oxidation of alkenyl chlorides.
Scheme 87: Chlorine–deuterium exchange promoted by a palladium catalyst.
Scheme 88: Reaction of alkenyl chlorides with thiols in the presence of AIBN (azobisisobutyronitrile).
Scheme 89: Chloroalkene annulation.
Carbenoid-mediated nucleophilic “hydrolysis” of 2-(dichloromethylidene)-1,1,3,3-tetramethylindane with DMSO participation, affording access to one-sidedly overcrowded ketone and bromoalkene descendants§
- Rudolf Knorr,
- Thomas Menke,
- Johannes Freudenreich and
- Claudio Pires
Beilstein J. Org. Chem. 2014, 10, 307–315, doi:10.3762/bjoc.10.28
- -reducing side-reactions to consume the aryllithium reagents 34a,b to some extent, as delineated below. Therefore, acid 10 was treated with an excess of 34a,b which were generated from aryl bromides, using either 2.5 equivalents thereof together with tert-butyllithium (t-BuLi, five equiv) or four
- equivalents of both aryl bromide and n-BuLi. The preformed sodium carboxylate of 10 in place of 36 was apparently too insoluble in Et2O to react with 34. The primary products 35 tend to eliminate Li2O slowly with formation of ketones 38 in the presence of aryllithium reagents 34 which will rapidly add to 38
- , creating the tertiary alcohols 39. The unwanted side-products 39 might also arise during simple aqueous work-up where hydrolytic ketone formation from primary products such as 35 was often [40][41] able to compete with the fast protolysis of residual aryllithium reagents. To avoid this suspected mischief
Graphical Abstract
Scheme 1: 1,1,3,3-Tetramethylindane derivatives are preferable.
Scheme 2: “Hydrolysis” of 6, and the KOR/dimsyl-K (11) system.
Scheme 3: Proposed carbenoid pathway from 6 to acid 10 and dimethyl sulfide (Me2S) in DMSO as the solvent.
Scheme 4: Proposed pathway to the main side-product 23 formed by nucleophilic addition of 11 to C-2 of 6.
Scheme 5: Possible course of the carbenoid chain reaction of 12 with DMSO and the α,α-dichloroalkene 6.
Scheme 6: Synthesis of the one-sidedly overcrowded descendants 38, 39, and 42.
Ring-opening reaction of 2,5-dioctyldithieno[2,3-b:3',2'-d]thiophene in the presence of aryllithium reagents
- Hao Zhong,
- Jianwu Shi,
- Jianxun Kang,
- Shaomin Wang,
- Xinming Liu and
- Hua Wang
Beilstein J. Org. Chem. 2013, 9, 767–774, doi:10.3762/bjoc.9.87
- between the structures of aryl groups and the efficiency of ring-opening reactions are discussed. Keywords: aryllithium reagents; 2'-arylthio-3,3'-bithiophene-2-carbaldehyde; dithieno[2,3-b:3',2'-d]thiophene; nucleophilicity; ring-opening reaction; Introduction Due to the promising optical and
- (1) with nine aryllithium reagents and the characterization of the nine corresponding ring-opening products. These studies should facilitate the understanding of the chemical stability of dithieno[2,3-b:3',2'-d]thiophene, which may be of importance in both organic chemistry and materials science
- . Furthermore, we show a novel method for the synthesis of 2'-arylthio-3,3'-bithiophene-2-carbaldehydes based on the ring-opening reaction. Results and Discussion Ring-opening reaction of 2,5-dioctyldithieno[2,3-b:3',2'-d]thiophene in the presence of aryllithium reagents The aryllithium reagents (Ar–Li) were
Graphical Abstract
Scheme 1: The ring-opening reaction of symmetric 2,5-disubstituted-dithieno[2,3-b:3',2'-d]thiophenes in the p...
Scheme 2: The ring-opening reaction of 1 in the presence of n-BuLi and t-BuLi employed for metal–halogen exch...
Figure 1: Crystallographic structure of 3i (left, top view) and crystal packing (right). Carbon, silicon, oxy...
Inter- and intramolecular enantioselective carbolithiation reactions
- Asier Gómez-SanJuan,
- Nuria Sotomayor and
- Esther Lete
Beilstein J. Org. Chem. 2013, 9, 313–322, doi:10.3762/bjoc.9.36
- enantioselectivity. The addition of TMEDA increases the rate of racemization, resulting in an inversion of diastereoselectivity to obtain 36, albeit in racemic form [44]. The enantioselective cycloisomerization of achiral organolithiums in the presence of a chiral ligand has been reported with aryllithium reagents
Graphical Abstract
Scheme 1: Intermolecular carbolithiation.
Scheme 2: Carbolithiation of cinnamyl and dienyl derivatives.
Scheme 3: Carbolithiation of cinnamyl alcohol.
Scheme 4: Carbolithiation of styrene derivatives.
Scheme 5: Carbolithiation of α-aryl O-alkenyl carbamates.
Scheme 6: Carbolithiation-rearrangement of N-alkenyl-N-arylureas.
Scheme 7: Carbolithiation of N,N-dimethylaminofulvene.
Scheme 8: Carbolithiation of enynes.
Scheme 9: Intramolecular carbolithiation.
Scheme 10: Carbolithiation of 5-alkenylcarbamates.
Scheme 11: Carbolithiation of cinnamylpiperidines.
Scheme 12: Carbolithiation of alkenylpyrrolidines.
Scheme 13: Enantioselective carbolithiation of N-allyl-2-bromoanilines.
Scheme 14: Effect of the ligand in the carbolithiation reaction.
Scheme 15: Effect of the alkene substitution in the carbolithiation reaction.
Scheme 16: Effect of the ring substitution in the carbolithiation reaction.
Scheme 17: Enantioselective carbolithiation of allyl aryl ethers.
Scheme 18: Formation of six-membered rings: pyrroloisoquinolines.
Scheme 19: Formation of six-membered rings: tetrahydroquinolines.
Alkoxide-induced ring opening of bicyclic 2-vinylcyclobutanones: A convenient synthesis of 2-vinyl-substituted 3-cycloalkene-1-carboxylic acid esters
- Xiufang Ji,
- Zhiming Li,
- Quanrui Wang and
- Andreas Goeke
Beilstein J. Org. Chem. 2012, 8, 650–657, doi:10.3762/bjoc.8.72
- ketones. The reaction was triggered by an in situ alkylation with alkyl or aryllithium reagents in the presence of catalytic amounts of Li-chelating agents (e.g., Scheme 1) [24]. The configuration of the newly formed double bond in position 6 was diastereoselectively determined by the configuration of the
Graphical Abstract
Scheme 1: Metathetic ring opening of 7-methyl-7-vinylbicyclo[3.2.0]hept-2-en-6-one to a linear polyene ketone....
Scheme 2: Synthesis of vinyl or phenyl substituted cyclobutanones 4a–i.
Figure 1: Determination of the structure of 3-phenyl-2-vinyl substituted cyclobutanone 4g.
Scheme 3: Ring opening of cyclobutanones 4 to afford products 5 or 6.
Scheme 4: Reaction of 4a with LDA.
Scheme 5: Plausible mechanism for ring opening of 4a.
