Catalysis

Directed, Nickel-Catalyzed 1,2-Alkylsulfenylation of Alkenyl Carbonyl Compounds

Authors

  • Zi-Qi Li The Scripps Research Institute - United States ,
  • Wen-Ji He The Scripps Research Institute - United States ,
  • Hui-Qi Ni The Scripps Research Institute - United States ,
  • Keary Engle The Scripps Research Institute - United States

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 on to 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 a variety 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.

Content

Thumbnail image of Manuscript.pdf

Supplementary material

Thumbnail image of Supporting Info.pdf
Supporting Information
experimental procedures, characterization data for new compounds, computational details, copies of NMR spectra
Thumbnail image of 3a.cif
3a_CIF
Crystallographic Information File for Compound 3a
Thumbnail image of S10.cif
S10_CIF
Crystallographic Information File for Compound S10
Thumbnail image of NMR Data (MNova Format).zip
NMR Data
NMR Data in MNova Format