Regioselective and Stereospecific Rhodium-Catalyzed Allylic Cyanomethylation with an Acetonitrile Equivalent: Construction of Acyclic β-Quaternary Stereogenic Nitriles
Mai-Jan Tom, P. Andrew Evans
Abstract
A 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.
Topics & Concepts
StereocenterChemistryRegioselectivityAcetonitrileAllylic rearrangementStereospecificityRhodiumCatalysisStereochemistryMedicinal chemistryOrganic chemistryEnantioselective synthesisCatalytic C–H Functionalization MethodsAsymmetric Hydrogenation and CatalysisAsymmetric Synthesis and Catalysis