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.

中文翻译：

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通过笼式限制可见光光催化解锁 Tropolone 的光环加成反应性，用于多级选择性转化


包含多个反应位点的有机化合物的精确不对称光化学转变为合成化学带来了重大进展。在此，我们报道了通过使用手性光活性金属-有机笼 （cPMOC） 作为酶模拟多口袋光催化剂，对流层酮环状三烯衍生物进行了前所未有的可见光诱导级联转化。笼式限制光催化促进了三个连续的基本步骤，即对映选择性 [2 + 2] 光环加成反应与查尔酮、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，导致具有多手性中心的双环 [3.2.2] 壬烷骨架通过其他方法无法实现。本研究展示了如何通过笼限超分子催化巧妙地操纵周围、化学和立体选择性的复杂合成挑战，以探索新的反应性。