A Highly Enantio- and Diastereoselective Molybdenum-Catalyzed Asymmetric Allylic Alkylation of Cyanoester

Conditions:
10 mol% Mo(CO)6, 15 mol% ligand, 10 mol% NaH, BSA, THF, 60 deg C
99% yield, 20/1 Branched/Linear, 11/1 dr, 97% ee

Barry M. Trost, John R. Miller, and Christopher M. Hoffman, Jr
J. Am. Chem. Soc., 2011, 133, 8165–8167

DOI: 10.1021/ja2029602

Summary: An efficacious Mo-catalyzed enantioselective allylation of various cyanoester nucleophiles provided a number of highly functionalized branched cyanoesters containing a quaternary carbon stereocenter.  This synthetic method generates the desired allylic cyanoesters products with high yield, chemoselectivity, diastereoselectivity and enantioselectivity.