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Keywords:

  • alkylation;
  • Grignard reaction;
  • nitriles;
  • quaternary centers;
  • sulfinyls;
  • exchange interactions

Abstract

Adding organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl–metal exchange to afford N- or C-metalated nitriles. Sulfinyl–magnesium exchange–alkylations efficiently install quaternary and tertiary centers, even in the case of tertiary sulfinylnitriles that contain a highly acidic methine proton. α-Sulfinylalkenenitriles afford moderately nucleophilic magnesiated nitriles, and the reactivity can be dramatically increased by conversion to the corresponding magnesiates. The sulfinyl-metal exchange is extremely fast, proceeds efficiently with quaternary, tertiary, and vinylic α-sulfinylnitriles, and exhibits an exceptional functional group tolerance in nitrile alkylations.