Chen Jie, Huang Yin-Hui, Yang Jie, Huang Yongxian, Lu Yu-Lin, Jiao Zhiwei, Su Cheng-Yong
MOE Laboratory of Bioinorganic and Synthetic Chemistry, GBRCE for Functional Molecular Engineering, LIFM, IGCME, School of Chemistry, Sun Yat-Sen University, Guangzhou 510275, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
J Am Chem Soc. 2024 Nov 27;146(47):32738-32747. doi: 10.1021/jacs.4c12290. Epub 2024 Nov 14.
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, ., 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.
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是合成化学领域的重大进展。在此，我们报道了一种前所未有的可见光诱导的托酚酮环状三烯衍生物的级联转化反应，该反应使用手性光活性金属有机笼（cPMOCs）作为模拟酶的多口袋光催化剂。笼限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]光环加成反应、区域和非对映选择性α-酮醇重排反应以及立体选择性1,3-酰基迁移反应，从而生成了具有多个手性中心的双环[3.2.2]壬烷骨架，这是其他方法无法实现的。这项研究展示了如何通过笼限超分子催化巧妙地操控周环、化学和立体选择性等复杂的合成挑战，以探索新的反应活性。
