Atropisomeric Amides as Chiral Ligands: Using (−)-Sparteine-Directed Enantioselective Silylation to Control the Conformation of a Stereogenic Axis

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Abstract
An enantiomerically pure (1-trimethylsilyl)ethyl group, constructed by a (−)-sparteine-directed enantioselective quench of a laterally lithiated tertiary aromatic amide, exerts powerful thermodynamic control over the conformation of the adjacent tertiary amide substituent. Ortholithiation and functionalization of the amide in the 6-position allows the single amide conformer to be trapped as an enantiomerically and diastereoisomerically pure amide atropisomer. Protodesilylation of the amide gives functionalized atropisomeric amides with a stereogenic axis of single absolute configuration, whose barriers to racemization have been determined by polarimetry. Enantiomerically pure amides bearing phosphine substituents are effective ligands in a Pd-catalyzed allylic substitution reactionthe first use of a nonbiaryl atropisomer as a chiral ligandand give products with 90% ee. The rate of racemization of the phosphine-substituted amide is powerfully influenced by the presence of palladium.