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理解光催化[2+2]环加成反应中三重态-三重态能量转移的机制：来自量子化学建模的见解

Understanding the Mechanism of Triplet-Triplet Energy Transfer in the Photocatalytic [2 + 2] Cycloaddition: Insights From Quantum Chemical Modeling.

作者信息

Lee Eunji, Moon Hyejin, Park Jiyong, Baik Mu-Hyun

机构信息

Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Republic of Korea.

Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon, Republic of Korea.

出版信息

J Comput Chem. 2025 Jun 15;46(16):e70155. doi: 10.1002/jcc.70155.

DOI:10.1002/jcc.70155
PMID:40497355
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC12152828/
Abstract

We investigate the mechanism of [2 + 2] photocycloaddition reaction of 3-(but-3-enyl)oxyquinolone using a chiral xanthone-containing triplet sensitizer. Quantum chemical computer models were utilized to examine the substrate-catalyst encounter complex structures, which were classified into syn- and anti-adducts. The photoactivation steps of the substrate were analyzed based on the Marcus equation of electron transfer, including intersystem crossings (ISC) and outer sphere triplet-triplet energy transfer (TTEnT). Our results show that the calculated rates of ISC are comparable for the two adducts, while the rates of TTEnT differ due to the orbital overlap between the donor and acceptor sites. After the TTEnT, a stereospecific cyclization occurs, completing the catalytic cycle. We propose a strategy to improve stereoselectivity by exploiting the intrinsic difference in TTEnT rates between the two encounter complex isomers.

摘要

我们使用含手性呫吨酮的三重态敏化剂研究了3-(丁-3-烯基)氧基喹诺酮的[2 + 2]光环加成反应机理。利用量子化学计算机模型研究了底物 - 催化剂遭遇络合物结构，其分为顺式和反式加合物。基于电子转移的Marcus方程分析了底物的光活化步骤，包括系间窜越（ISC）和外层三重态 - 三重态能量转移（TTEnT）。我们的结果表明，两种加合物的ISC计算速率相当，而TTEnT速率因供体和受体位点之间的轨道重叠而不同。在TTEnT之后，发生立体特异性环化，完成催化循环。我们提出了一种策略，通过利用两种遭遇络合物异构体之间TTEnT速率的内在差异来提高立体选择性。

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