Pd/Cu-Cocatalyzed Enantio- and Diastereodivergent Wacker-Type Dicarbofunctionalization of Unactivated Alkenes

The Wacker and Wacker-type reactions are some of the most fundamental and powerful transformations in organic chemistry for their ability to efficiently produce valuable chemicals. Remarkable progress has been achieved in asymmetric oxy/aza-Wacker-type reactions; however, asymmetric Wacker-type dicarbofunctionalization remains underdeveloped, especially for the concurrent construction of two stereocenters. Herein, we report a Pd/Cu-cocatalyzed enantio- and diastereodivergent Wacker-type dicarbofunctionalization of alkene-tethered aryl triflates with imino esters. A series of 2-indanyl motifs bearing adjacent carbon stereocenters could be easily synthesized in moderate to excellent yields and with good to excellent diastereo- and enantioselectivities (up to >20:1 dr and >99% ee). Density functional theory calculations revealed that the origin of diastereoselectivity in this Pd/Cu synergistic catalytic system is jointly determined by both the intermolecular <i>anti</i>-carbopalladation of alkenes and the reductive elimination processes, in accordance with the Curtin-Hammett principle.