Directed, nickel-catalyzed 1, 2-alkylsulfenylation of alkenyl carbonyl compounds. Issue 22 (19th May 2022)

• Record Type: Journal Article
• Authors: Li, Zi-Qi; He, Wen-Ji; Ni, Hui-Qi; Engle, Keary M.
• Is Part Of: Chemical science. Volume 13:Issue 22(2022)
• Page Start: 6567
• Page End: 6572
• Publication Date: 2022-05-19
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc01563c
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Electrophilic sulfenylating agents enable the three-component nickel-catalyzed 1, 2-alkylsulfenylation of alkenyl carbonyl compounds with high regio- and diastereoselectivity. Abstract : We report a regioselective, nickel-catalyzed syn -1, 2-carbosulfenylation of non-conjugated alkenyl carbonyl compounds with alkyl/arylzinc nucleophiles and tailored N–S electrophiles. This method allows the simultaneous installation of a variety of C(sp 3 ) and S(Ar) (or Se(Ar)) groups onto unactivated alkenes, which complements previously developed 1, 2-carbosulfenylation methodology in which only C(sp 2 ) nucleophiles are compatible. A bidentate directing auxiliary controls regioselectivity, promotes high syn -stereoselectivity with a variety of E - and Z -internal alkenes, and enables the use of an array of electrophilic sulfenyl (and seleno) electrophiles. Among compatible electrophiles, those with N -alkyl-benzamide leaving groups were found to be especially effective, as determined through comprehensive structure–reactivity mapping.