Visible-light excitation of iminium ions enables the enantioselective catalytic ?-alkylation of enals

Silvi, Mattia; Verrier, Charlie; Rey, Yannick P.; Buzzetti, Luca; Melchiorre, Paolo

Abstract

© 2017 Macmillan Publishers Limited, part of Springer Nature. All rights reserved. Chiral iminium ions - generated upon condensation of α,β-unsaturated aldehydes and amine catalysts - are used extensively by chemists to make chiral molecules in enantioenriched form. In contrast, their potential to absorb light and promote stereocontrolled photochemical processes remains unexplored. This is despite the fact that visible-light absorption by iminium ions is a naturally occurring event that triggers the mechanism of vision in higher organisms. Herein we demonstrate that the direct excitation of chiral iminium ions can unlock unconventional reaction pathways, enabling enantioselective catalytic photochemical β-alkylations of enals that cannot be realized via thermal activation. The chemistry uses readily available alkyl silanes, which are recalcitrant to classical conjugate additions, and occurs under illumination by visible-light-emitting diodes. Crucial to success was the design of a chiral amine catalyst with well-tailored electronic properties that can generate a photo-active iminium ion while providing the source of stereochemical induction. This strategy is expected to offer new opportunities for reaction design in the field of enantioselective catalytic photochemistry.

• Journal Article Type: Article
• Acceptance Date: Feb 7, 2017
• Online Publication Date: Mar 20, 2017
• Publication Date: 2017-09
• Deposit Date: Jan 29, 2020
• Journal: Nature Chemistry
• Print ISSN: 1755-4330
• Electronic ISSN: 1755-4349
• Publisher: Nature Publishing Group
• Peer Reviewed: Peer Reviewed
• Volume: 9
• Issue: 9
• Pages: 868-873
• DOI: https://doi.org/10.1038/nchem.2748
• Public URL: https://nottingham-repository.worktribe.com/output/3826268
• Publisher URL: https://www.nature.com/articles/nchem.2748
• Additional Information: Received: 20 September 2016; Accepted: 7 February 2017; First Online: 20 March 2017; : The authors declare no competing financial interests.