Visible light-driven conjunctive olefination

Filippini, Dario; Silvi, Mattia

Abstract

Carboxylic acids and aldehydes are ubiquitous in chemistry and are native functionalities in many bioactive molecules and natural products. As such, a general cross-coupling process that involves these partners would open new avenues to achieve molecular diversity. Here we report a visible-light-mediated and transition metal-free conjunctive olefination that uses an alkene ‘linchpin’ with a defined geometry to cross-couple complex molecular scaffolds that contain carboxylic acids and aldehydes. The chemistry merges two cornerstones of organic synthesis—namely, the Wittig reaction and photoredox catalysis—in a catalytic cycle that couples a radical addition process with the redox generation of a phosphonium ylide. The methodology allows the rapid structural diversification of bioactive molecules and natural products in a native form, with a high functional group tolerance, and also forges a new alkene functional group with a programmable E–Z stereochemistry.

Citation

Filippini, D., & Silvi, M. (2022). Visible light-driven conjunctive olefination. Nature Chemistry, 14(1), 66-70. https://doi.org/10.1038/s41557-021-00807-x

• Journal Article Type: Article
• Acceptance Date: Sep 3, 2021
• Online Publication Date: Nov 4, 2021
• Publication Date: Jan 1, 2022
• Deposit Date: Dec 6, 2021
• Publicly Available Date: May 5, 2022
• Journal: Nature Chemistry
• Print ISSN: 1755-4330
• Electronic ISSN: 1755-4349
• Publisher: Nature Publishing Group
• Peer Reviewed: Peer Reviewed
• Volume: 14
• Issue: 1
• Pages: 66-70
• DOI: https://doi.org/10.1038/s41557-021-00807-x
• Keywords: General Chemical Engineering; General Chemistry
• Public URL: https://nottingham-repository.worktribe.com/output/6908395
• Publisher URL: https://www.nature.com/articles/s41557-021-00807-x