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Cooperative Palladium/Lewis Acid-Catalyzed Transfer Hydrocyanation of Alkenes and Alkynes Using 1‑Methylcyclohexa-2,5-diene-1-carbonitrile
journal contribution
posted on 2018-11-04, 00:00 authored by Anup Bhunia, Klaus Bergander, Armido StuderCatalytic transfer
hydrocyanation represents a clean and safe alternative
to hydrocyanation processes using toxic HCN gas. Such reactions provide
access to pharmaceutically important nitrile derivatives starting
with alkenes and alkynes. Herein, an efficient and practical cooperative
palladium/Lewis acid-catalyzed transfer hydrocyanation of alkenes
and alkynes is presented using 1-methylcyclohexa-2,5-diene-1-carbonitrile
as a benign and readily available HCN source. A large set of nitrile
derivatives (>50 examples) are prepared from both aliphatic and
aromatic
alkenes with good to excellent anti-Markovnikov selectivity. A range
of aliphatic alkenes engage in selective hydrocyanation to provide
the corresponding nitriles. The introduced method is useful for chain
walking hydrocyanation of internal alkenes to afford terminal nitriles
in good regioselectivities. This protocol is also applicable to late-stage
modification of bioactive molecules.