Asymmetric Photochemical [2 + 2]-Cycloaddition of Acyclic Vinylpyridines through Ternary Complex Formation and an Uncontrolled Sensitization MechanismClick to copy article linkArticle link copied!
- Zebediah C. GirvinZebediah C. GirvinDepartment of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut06511, United StatesMore by Zebediah C. Girvin
- Laura F. CotterLaura F. CotterDepartment of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut06511, United StatesMore by Laura F. Cotter
- Hyung YoonHyung YoonDepartment of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut06511, United StatesMore by Hyung Yoon
- Steven J. ChapmanSteven J. ChapmanDepartment of Chemistry, University of Wisconsin─Madison, 1101 University Avenue, Madison, Wisconsin53706, United StatesMore by Steven J. Chapman
- James M. Mayer*James M. Mayer*E-mail: [email protected] (J.M.M.)Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut06511, United StatesMore by James M. Mayer
- Tehshik P. Yoon*Tehshik P. Yoon*E-mail: [email protected] (T.P.Y.)Department of Chemistry, University of Wisconsin─Madison, 1101 University Avenue, Madison, Wisconsin53706, United StatesMore by Tehshik P. Yoon
- Scott J. Miller*Scott J. Miller*E-mail: [email protected] (S.J.M.)Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut06511, United StatesMore by Scott J. Miller
Abstract

Stereochemical control of photochemical reactions that occur via triplet energy transfer remains a challenge. Suppressing off-catalyst stereorandom reactivity is difficult for highly reactive open-shell intermediates. Strategies for suppressing racemate-producing, off-catalyst pathways have long focused on formation of ground state, substrate-catalyst chiral complexes that are primed for triplet energy transfer via a photocatalyst in contrast to their off-catalyst counterparts. Herein, we describe a strategy where both a chiral catalyst-associated vinylpyridine and a nonassociated, free vinylpyridine substrate can be sensitized by an Ir(III) photocatalyst, yet high levels of diastereo- and enantioselectivity in a [2 + 2] photocycloaddition are achieved through a preferred, highly organized transition state. This mechanistic paradigm is distinct from, yet complementary to current approaches for achieving high levels of stereocontrol in photochemical transformations.
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