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Reductive C−C Coupling from α,β‐Unsaturated Nitriles by Intercepting Keteniminates
Author(s) -
Hale Lillian V. A.,
Sikes N. Marianne,
Szymczak Nathaniel K.
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201904530
Subject(s) - chemistry , nitrile , catalysis , hydride , electrophile , transfer hydrogenation , combinatorial chemistry , pincer movement , hydrogen , reductive elimination , coupling (piping) , organic chemistry , photochemistry , ruthenium , materials science , metallurgy
We present an atom‐economic strategy to catalytically generate and intercept nitrile anion equivalents using hydrogen transfer catalysis. Addition of α,β‐unsaturated nitriles to a pincer‐based Ru−H complex affords structurally characterized κ‐N‐coordinated keteniminates by selective 1,4‐hydride transfer. When generated in situ under catalytic hydrogenation conditions, electrophilic addition to the keteniminate was achieved using anhydrides to provide α‐cyanoacetates in high yields. This work represents a new application of hydrogen transfer catalysis using α,β‐unsaturated nitriles for reductive C−C coupling reactions.