Photochemical [2+4]‐Dimerization Reaction from the Excited State
Photochemical [2+4]‐Dimerization Reaction from the Excited State
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光化学 [2 4] — 激发态的二聚反应
DOI：
10.1002/anie.202316662
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Sivaguru, Jayaraman
中科院分区：
文献类型：
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作者：
Ahuja, Sapna;Baburaj, Sruthy;Valloli, Lakshmy Kannadi;Rakhimov, Sarvar Aminovich;Manal, Kavyasree;Kushwaha, Aakrati;Jockusch, Steffen;Forbes, Malcolm D. E.;Sivaguru, Jayaraman
芳基马来酰亚胺在可见光直接照射和敏化能量转移条件下发生新型[2+4]-光二聚反应，而不是预期的[2+2]-光二聚反应。通过光化学、光物理和光谱研究，我们可以解释芳基马来酰亚胺中这种新的激发态反应性。光二聚体的立体化学取决于光二聚化过程中普遍存在的非键合相互作用的类型，这反过来又由马来酰亚胺环上的取代基决定。更重要的是，所形成的光二聚体的立体化学与在热条件下观察到的产物互补。
Aryl‐maleimides undergo a novel [2+4]‐photodimerization instead of the expected [2+2]‐photodimerization under both direct irradiation with visible light and under sensitized energy transfer conditions. This new excited state reactivity in aryl‐maleimides is deciphered through photochemical, photophysical, and spectroscopic studies. The stereochemistry of the photodimer depends on the type of non‐bonding interactions prevalent during photodimerization which is in turn dictated by the substituents on the maleimide ring. More importantly, the stereochemistry of the photodimer formed is complementary to the product observed under thermal conditions.