Desymmetrization of Cyclic Sulfonimidamides by Asymmetric Allylation
David A. Gutierrez, Garrett Toth-Williams, Croix J. Laconsay, Michael Yasuda, James C. Fettinger, Michael J. Di Maso, Jared T. Shaw
Abstract
Herein we report the first transition metal-catalyzed approach to the enantioenriched synthesis of cyclic sulfonimidamides relying on commercially available palladium catalysts and ligands. High-throughput experimentation (HTE) was employed to identify the optimal catalyst system and solvent. The method is applied to a variety of saturated and unsaturated rings and exhibits the highest selectivity for 2-substituted allyl electrophiles. The products are further elaborated to complex, tricyclic scaffolds. DFT experiments presented herein highlight the key ligand substrate interactions leading to the high levels of enantioselectivity.