A highly enantioselective rhodium-catalyzed allylic alkylation of acyclic a-alkoxy aryl ketones utilizing the complex derived from Wilkinson's catalyst and the chiral monodentate phosphite, BINOL-MeOP, has been developed. This process represents the first enantioselective rhodium-catalyzed allylic substitution with a prochiral nucleophile. The ability to transform the aryl ketones into the corresponding alcohol and ester illustrates the potential utility of this transformation for target directed synthesis.

The asymmetric synthesis of allylic amines is an important research area in modern synthetic organic chemistry, primarily due to the inherent utility and ubiquity of this functional group in various synthetic intermediates and bioactive agents. For instance, a plethora of methods for the stereocontrolled construction of allylic amines now provides a vibrant array of strategies for the installation of this important functionality. This review highlights developments in the field since 1998 through the provision of the most important methods and their mechanistic aspects in order to provide insight into their current scope and limitations. Hence, we envisage it will be an essential guide to the current state-of-the-art for this important area, which highlights potential new opportunities for further developments.

The transition metal catalyzed allylic amination represents a powerful and versatile cross-coupling for the asymmetric construction of stereogenic C-N bonds that are present in secondary metabolites and medicinally important agents. We have developed a regio- and enantiospecific rhodium-catalyzed allylic amination reaction using the aza-ylide derived from 1-aminopyridinium iodide. This investigation demonstrates the importance of the ylide-stabilizing group for obtaining the desired nucleophilicity and the ability to utilize the aza-ylide as a commercially available ammonia equivalent, which serves to illustrate the synthetic potential of this nucleophile for the preparation of primary amines. Overall, this work provides an opportunity to investigate the utility of this new class of nucleophiles in related metal-catalyzed reactions.

We have devised a highly regio- and enantioselective iridium-catalyzed allylic amination reaction with the sulfur-stabilized aza-ylide, S,S-diphenylsulfilimine.