Direct Visible-Light-Excited Asymmetric Lewis Acid Catalysis of Intermolecular [2+2] Photocycloadditions

Xiaoqiang Huang(Philipps University of Marburg), Taylor R. Quinn(University of Notre Dame), Klaus Harms(Philipps University of Marburg), Richard D. Webster(Nanyang Technological University), Lilu Zhang(Philipps University of Marburg), Olaf Wiest(University of Notre Dame), Eric Meggers(Philipps University of Marburg)
Journal of the American Chemical Society
June 23, 2017
Cited by 267Open Access
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Abstract

A reaction design is reported in which a substrate-bound chiral Lewis acid complex absorbs visible light and generates an excited state that directly reacts with a cosubstrate in a highly stereocontrolled fashion. Specifically, a chiral rhodium complex catalyzes visible-light-activated intermolecular [2+2] cycloadditions, providing a wide range of cyclobutanes with up to >99% ee and up to >20:1 d.r. Noteworthy is the ability to create vicinal all-carbon-quaternary stereocenters including spiro centers in an intermolecular fashion.


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