中山大学苏成勇团队报道了笼式可见光催化多级选择性转化，释放环庚三烯酚酮的光环加成反应性。相关研究成果发表在2024年11月14日出版的《美国化学会杂志》。

含有多个反应位点的有机化合物的精确不对称光化学转化，在合成化学方面取得了重大进展。

该文中，研究人员报告了一种前所未有的可见光诱导的，环庚三烯酚酮环三烯衍生物的级联转化反应，该转化是通过使用手性光活性金属有机笼（cPMOCs），作为模拟酶的多阴极光催化剂实现的。

笼式光催化促进了三个连续的基本步骤，即与查尔酮的对映选择性[2+2]光环加成、区域和非对映选择性α-酮重排，以及立体选择性1,3-酰基转移，从而产生具有多手性中心的双环[3.2.2]壬烷骨架，这是其他方法无法实现的。

该研究展示了笼式超分子催化如何巧妙地，操纵围选择性、化学选择性和立体选择性的复杂合成挑战，以探索新的反应性。

附：英文原文

Title: Unlocking Photocycloaddition Reactivity of Tropolone by Cage-Confined Visible-Light Photocatalysis for Multilevel Selective Transformation

Author: Jie Chen, Yin-Hui Huang, Jie Yang, Yongxian Huang, Yu-Lin Lu, Zhiwei Jiao, Cheng-Yong Su

Issue&Volume: November 14, 2024

Abstract: The precise asymmetric photochemical transformation of organic compounds containing multiple reactive sites presents significant progress in synthetic chemistry. Herein, we report an unprecedented visible-light-induced cascade transformation of tropolone cyclic triene derivatives by using chiral photoactive metal–organic cages (cPMOCs) as enzyme-mimicking multipocket photocatalysts. The cage-confined photocatalysis promotes three successive elementary steps, i.e., enantioselective [2 + 2] photocycloaddition with chalcone, regio-, and diastereoselective α-ketol rearrangement, and a stereoselective 1,3-acyl shift, resulting in bicyclo[3.2.2]nonane skeleton with multichiral-centers unattainable by other methods. This study demonstrates how complex synthetic challenges of peri-, chemo-, and stereoselectivities could be subtly manipulated by cage-confined supramolecular catalysis for exploration of new reactivities.

DOI: 10.1021/jacs.4c12290

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c12290