Photoinduced Rearrangement of Dienones and Santonin Rerouted by Amines

Zhipeng Zhang; Maxim Ratnikov; Glen Spraggon; Phil B Alper

doi:10.1002/anie.201710463

Photoinduced Rearrangement of Dienones and Santonin Rerouted by Amines

Angew Chem Int Ed Engl. 2018 Jan 22;57(4):904-908. doi: 10.1002/anie.201710463. Epub 2017 Dec 20.

Authors

Zhipeng Zhang¹, Maxim Ratnikov¹, Glen Spraggon¹, Phil B Alper¹

Affiliation

¹ Department of Discovery Chemistry, Genomics Institute of the Novartis Research Foundation, San Diego, CA, 92121, USA.

PMID: 29266649
DOI: 10.1002/anie.201710463

Abstract

The photoinduced rearrangement pathways of simple 2,5-dienones and the natural product santonin were found to be effectively rerouted by amines, giving rise to unprecedented products. Either cis olefins or cyclobutenes were obtained from 4,4-disubstituted 2,5-dienone upon irradiation (365 nm) in the presence of various amines depending on the solvent. Previously undescribed [4.4.0] and [5.3.0] fused-ring-containing products were obtained when santonin was irradiated (365 nm) in the presence of methylamine. The amines present in these reactions were incorporated into the products by means of amide-group formation.

Keywords: dienones; natural products; photochemistry; rearrangement; santonin.

Publication types

Research Support, Non-U.S. Gov't