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Angew Chem Int Ed Engl
; 58(25): 8531-8535, 2019 Jun 17.
Article
in English
| MEDLINE
| ID: mdl-31016843
ABSTRACT
We present an atom-economic strategy to catalytically generate and intercept nitrile anion equivalents using hydrogen transfer catalysis. Addition of α,ß-unsaturated nitriles to a pincer-based Ru-H complex affords structurally characterized κ-N-coordinated keteniminates by selective 1,4-hydride transfer. When generated inâ 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,ß-unsaturated nitriles for reductive C-C coupling reactions.