Jian Lv, Qichao Zhang, Xingren Zhong, and Sanzhong Luo*

Stable carbocations such as tritylium ions have been widely explored as organic Lewis acid catalysts and reagents in organic synthesis. However, achieving asymmetric carbocation catalysis remains elusive ever since they were first identified over one century ago. The challenges mainly come from their limited compatibility, scarcity of chiral carbocations, as well as the extremely low barrier to racemization of chiral carbenium ions. We reported here a latent concept for asymmetric carbocation catalysis. In this strategy, chiral trityl phosphate is employed as the carbocation precursor, which undergoes facile ionic dissociation upon mild external stimulation (e.g., acid, H-bonding, polar substrates) to form a catalytically active chiral ion pair for substrate activation and chiral induction. The latent strategy provides a solution for the long sought-after asymmetric carbocation catalysis as illustrated in three different enantioselective transformations.

This work has been published in J. Am. Chem. Soc., 2015, 137, 15576–15583.