The 2-azaallyl anion is one of the earliest known intermediates in synthetic organic chemistry, tracing its roots back to a 19th-century report from Erlenmeyer. The past decade has witnessed significant renewed interest in <i>semi-stabilized</i> 2-azaallyl anions, which possess at least two aromatic substituents on the terminal carbons, as intermediates toward the synthesis of alkaloid natural products and pharmaceutically-relevant scaffolds. Traditionally, generation of 2-azaallyl anions requires deprotonation of the conjugate acid with a strong base under anhydrous and, frequently, anaerobic reaction conditions. Our group, however, has focused on an alternative transition metal-catalyzed decarboxylative reaction manifold which allows for the generation and alkylation of semi-stabilized 2-azaallyl anions under a broader range of reaction conditions. This talk will recount recent advances from our group's efforts in this arena including the development of a Pd-catalyzed enantioselective decarboxylative propargylation and a branched-selective decarboxylative prenylation of diphenylglycinate imino esters, as well as a Ni-catalyzed variant of our previously reported asymmetric decarboxylative allylation reaction. The influence of steric and electronic factors on the regioselectivity for the Pd(II)-mediated allylation of 1,1,3-triaryl-2-azaallyl anions will also be discussed.

Recent advances in the transition metal-catalyzed decarboxylative generation and alkylation of 2-azaallyl anions

253rd National Meeting (2017)

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