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Directed, nickel-catalyzed 1,2-alkylsulfenylation of alkenyl carbonyl compounds.

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(sp³) and S(Ar) (or Se(Ar)) groups onto unactivated alkenes, which complements previously developed 1,2-carbosulfenylation methodology in which only C(sp²) 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.

SUBMITTER: Li ZQ

PROVIDER: S-EPMC9172569 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

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Directed, nickel-catalyzed 1,2-alkylsulfenylation of alkenyl carbonyl compounds.

Li Zi-Qi ZQ He Wen-Ji WJ Ni Hui-Qi HQ Engle Keary M KM

Chemical science 20220502 22

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(sp3) and S(Ar) (or Se(Ar)) groups onto unactivated alkenes, which complements previously developed 1,2-carbosulfenylation methodology in which only C(sp2) nucleophiles are compatible. A bidentate directing auxiliary contro ...[more]

PMID: 35756518

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