Enantioselective synthesis of alkylidene cyclohexanes by an asymmetric olefination/cross‐coupling sequence

Denmark, Scott E.; Chen, Chien‐Tien ‐T

doi:10.1002/hc.520060207

Heteroatom Chemistry

1995

DOI: 10.1002/hc.520060207

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Enantioselective synthesis of alkylidene cyclohexanes by an asymmetric olefination/cross‐coupling sequence

Scott E. Denmark¹,

Chien‐Tien ‐T Chen²

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Cited by 6 publications

References 73 publications

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Cross‐Coupling Reaction of Alkenyl Sulfoximines and Alkenyl Aminosulfoxonium Salts with Organozincs by Dual Nickel Catalysis and Lewis Acid Promotion

Erdelmeier

Bülow

Woo

et al. 2019

Chemistry A European J

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In this article, the cross-coupling reaction( CCR) of exocyclic, axially chiral, and acyclic alkenyl (N-methyl)sulfoximines with alkyl-and arylzincs is described . The CCR generally requires dual Ni catalysis and MgBr 2 promotion, which is effective in diethyl ether but not in THF.N MR spectroscopy revealedacomplexation of alkenyl sulfoximines by MgBr 2 in diethyle ther,w hichs uggestsa na cceleration of the oxidative addition through nucleofugal activation.T he CCR of alkenyl sulfoximinesg enerally proceedsi nt he presence of Ni(dppp)Cl 2 as ap recatalyst and MgBr 2 with alkyl-and arylzincs with ah igh degree of stereoretention at the Ca nd the Sa tom. CCR of axially chirala lkenyl sulfoximinesw ith Ni(PPh 3 ) 2 Cl 2 as ap recatalyst and ZnPh 2 does not require salt promotion and is stereoretentive.T he reactionw ith Zn(CH 2 SiMe 3 ) 2 ,h owever,d emands salt promotion and is not stereoretentive. CCR of axially chiral a-methylated alkenyl sulfoximines affordedp ersubstituted axiallyc hiral alkenes with high selectivity.A lkenyl (N-triflyl)sulfoximines engage in as tereoretentive CCR with Grignard reagents and Ni(PPh 3 ) 2 Cl 2 .Ni-Catalyzed and MgBr 2 -promoted CCR of E-configured acyclica lkenyl sulfoximinesa nd aminosulfoxonium salts with ZnPh 2 andZ n(CH 2 SiMe 3 ) 2 is stereoretentivew ith Ni(dppp)Cl 2 and Ni(PPh 3 ) 2 Cl 2 .C CRs of acyclica lkenyls ulfoximinesa nd alkenyl aminosulfoxonium salts, carrying am ethyl groupa tt he a position, take ad ifferent course andg ive alkenyls ulfinamidesu nder stereoretention at the Sa nd C atom.C CR of acyclic, exocyclic, and axially chiral alkenyl sulfoximines has been successfully applied to the stereoselective synthesis of homoallylic alcohols, exocyclic alkenes, and axiallyc hiral alkenes, respectively.

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Cross‐Coupling Reaction of Alkenyl Sulfoximines and Alkenyl Aminosulfoxonium Salts with Organozincs by Dual Nickel Catalysis and Lewis Acid Promotion

Erdelmeier

Bülow

Woo

et al. 2019

Chemistry A European J

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Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums

Erdelmeier

Won

Park

et al. 2020

Chemistry A European J

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The mechanistic platform for a novel nickel0‐catalyzed anionic cross‐coupling reaction (ACCR) of lithium sulfonimidoyl alkylidene carbenoids (metalloalkenyl sulfoximines) with organometallic reagents is reported herein, affording substituted alkenylmetals and lithium sulfinamides. The Ni0‐catalyzed ACCR of three different types of metalloalkenyl sulfoximines, including acyclic, axially chiral and exocyclic derivatives, with sp2 organolithiums and sp2 and sp3 Grignard reagents has been studied. The ACCR of metalloalkenyl sulfoximines with PhLi in the presence of the Ni0‐catalyst and precatalyst Ni(PPh3)2Cl2 afforded alkenyllithiums, under inversion of configuration at the C atom and complete retention at the S atom. In a combination of experimental and DFT studies, we propose a catalytic cycle of the Ni0‐catalyzed ACCR of lithioalkenyl sulfoximines. Computational studies reveal two distinctive pathways of the ACCR, depending on whether a phosphine or 1,5‐cyclooctadiene (COD) is the ligand of the Ni atom. They rectify the underlying importance of forming the key Ni0‐vinylidene intermediate through an indispensable electron‐rich Ni0‐center coordinated by phosphine ligands. Fundamentally, we present a mechanistic study in controlling the diastereoselectivity of the alkenyllithium formation via the key lithium sulfinamide coordinated Ni0‐vinylidene complex, which consequently avoids an unselective formation of an alkylidene carbene Ni‐complex and ultimately racemic alkenyllithium.

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ChemInform Abstract: Enantioselective Synthesis of Alkylidene Cyclohexanes by an Asymmetric Olefination/Cross‐Coupling Sequence.

Denmark

Chen

1995

ChemInform

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Enantioselective synthesis of alkylidene cyclohexanes by an asymmetric olefination/cross‐coupling sequence

Cited by 6 publications

References 73 publications

Cross‐Coupling Reaction of Alkenyl Sulfoximines and Alkenyl Aminosulfoxonium Salts with Organozincs by Dual Nickel Catalysis and Lewis Acid Promotion

Cross‐Coupling Reaction of Alkenyl Sulfoximines and Alkenyl Aminosulfoxonium Salts with Organozincs by Dual Nickel Catalysis and Lewis Acid Promotion

Nickel‐Catalyzed Anionic Cross‐Coupling Reaction of Lithium Sulfonimidoyl Alkylidene Carbenoids With Organolithiums

ChemInform Abstract: Enantioselective Synthesis of Alkylidene Cyclohexanes by an Asymmetric Olefination/Cross‐Coupling Sequence.

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