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Sulfinylnitriles: Sulfinyl–Metal Exchange–Alkylation Strategies
Author(s) -
Nath Dinesh,
Fleming Fraser F.
Publication year - 2013
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.201203174
Subject(s) - chemistry , alkylation , reagent , nitrile , reactivity (psychology) , nucleophile , magnesium , metal , medicinal chemistry , combinatorial chemistry , organic chemistry , catalysis , medicine , alternative medicine , pathology
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.