A photochemical C=C cleavage process: toward access to backbone N-formyl peptides

Haopei Wang; Zachary T Ball

doi:10.3762/bjoc.17.202

A photochemical C=C cleavage process: toward access to backbone N-formyl peptides

Beilstein J Org Chem. 2021 Dec 15:17:2932-2938. doi: 10.3762/bjoc.17.202. eCollection 2021.

Authors

Haopei Wang¹, Zachary T Ball¹

Affiliation

¹ Department of Chemistry, Rice University, Houston TX, USA.

Abstract

Photo-responsive modifications and photo-uncaging concepts are useful for spatiotemporal control of peptides structure and function. While side chain photo-responsive modifications are relatively common, access to photo-responsive modifications of backbone N-H bonds is quite limited. This letter describes a new photocleavage pathway, affording N-formyl amides from vinylogous nitroaryl precursors under physiologically relevant conditions via a formal oxidative C=C cleavage. The N-formyl amide products have unique properties and reactivity, but are difficult or impossible to access by traditional synthetic approaches.

Keywords: formyl peptide; nitroaryl compound; nitroso compound; olefin cleavage; photocleavage.

Grants and funding

We acknowledge support from the Robert A. Welch Foundation Research Grant C-1680 (Z.T.B.), and the National Science Foundation under grant number CHE-1904865.