Photoinduced formal [4 + 2] cycloaddition of two electron-deficient olefins and its application to the synthesis of lucidumone.

Xu, Zhezhe; Peng, Weibo; Huang, Jiarui; Shen, Jinhui; Guo, Jing-Jing; Hu, Anhua · Nat Commun · 2024

basic_science · Level V

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Abstract

Electronically mismatched Diels-Alder reaction between two electron-deficient components is synthetically useful and yet underdeveloped under thermal conditions. Herein, a photoinduced formal [4 + 2] cycloaddition of enone with a variety of electron-deficient dienes is described. Key to the success of this stepwise methodology relies on a C - C bond cleavage/rearrangement of the cyclobutane based overbred intermediate via diversified mechanistic pathways. Based on this annulation method, total synthesis of lucidumone is achieved in nine steps.