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Cross‐Coupling Reaction of Alkenyl Sulfoximines and Alkenyl Aminosulfoxonium Salts with Organozincs by Dual Nickel Catalysis and Lewis Acid Promotion
Author(s) -
Erdelmeier Irene,
Bülow Gerd,
Woo ChangWan,
Decker Jürgen,
Raabe Gerhard,
Gais HansJoachim
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201901163
Subject(s) - chemistry , catalysis , medicinal chemistry , ether , alkyl , diethyl ether , reagent , lewis acids and bases , oxidative addition , salt (chemistry) , organic chemistry
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. NMR spectroscopy revealed a complexation of alkenyl sulfoximines by MgBr 2 in diethyl ether, which suggests an acceleration of the oxidative addition through nucleofugal activation. The CCR of alkenyl sulfoximines generally proceeds in the presence of Ni(dppp)Cl 2 as a precatalyst and MgBr 2 with alkyl‐ and arylzincs with a high degree of stereoretention at the C and the S atom. CCR of axially chiral alkenyl sulfoximines with Ni(PPh 3 ) 2 Cl 2 as a precatalyst and ZnPh 2 does not require salt promotion and is stereoretentive. The reaction with Zn(CH 2 SiMe 3 ) 2 , however, demands salt promotion and is not stereoretentive. CCR of axially chiral α‐methylated alkenyl sulfoximines afforded persubstituted axially chiral alkenes with high selectivity. Alkenyl ( N ‐triflyl)sulfoximines engage in a stereoretentive CCR with Grignard reagents and Ni(PPh 3 ) 2 Cl 2 . Ni‐Catalyzed and MgBr 2 ‐promoted CCR of E ‐configured acyclic alkenyl sulfoximines and aminosulfoxonium salts with ZnPh 2 and Zn(CH 2 SiMe 3 ) 2 is stereoretentive with Ni(dppp)Cl 2 and Ni(PPh 3 ) 2 Cl 2 . CCRs of acyclic alkenyl sulfoximines and alkenyl aminosulfoxonium salts, carrying a methyl group at the α position, take a different course and give alkenyl sulfinamides under stereoretention at the S and C atom. CCR of acyclic, exocyclic, and axially chiral alkenyl sulfoximines has been successfully applied to the stereoselective synthesis of homoallylic alcohols, exocyclic alkenes, and axially chiral alkenes, respectively.