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Regioselective and Stereospecific Rhodium-Catalyzed Allylic Cyanomethylation with an Acetonitrile Equivalent: Construction of Acyclic β‑Quaternary Stereogenic Nitriles
journal contribution
posted on 2020-07-02, 19:36 authored by Mai-Jan Tom, P. Andrew EvansA highly
regioselective and stereospecific rhodium-catalyzed
cyanomethylation of tertiary allylic carbonates for the
construction of acyclic β-quaternary stereogenic nitriles
is described. This protocol represents the first example of a metal-catalyzed
allylic substitution reaction using a triorganosilyl-stabilized
acetonitrile anion, which permits access to several carbonyl derivatives
that are challenging to prepare using conventional pronucleophiles.
The synthetic utility of the stereospecific cyanomethylation
is further exemplified through the construction of an intermediate
utilized in the total synthesis of both (−)-epilaurene and
(−)-α-cuparenone.