Transposed Paternò–Büchi Reaction

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• 作者：Elango KumarasamyRamya Raghunathan ; Sunil Kumar Kandappa ; A. Sreenithya ; Steffen Jockusch ; Raghavan B Sunoj ; J. Sivaguru
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：January 18, 2017
• 年：2017
• 卷：139
• 期：2
• 页码：655-662
• 全文大小：646K
• ISSN：1520-5126

文摘

A complementary strategy of utilizing ππ* excited state of alkene instead of nπ* excited state of the carbonyl chromophore in a “transposed Paternò–Büchi” reaction is evaluated with atropisomeric enamides as the model system. Based on photophysical investigations, the nature of excited states and the reactive pathway was deciphered leading to atropselective reaction. This new concept of switching of excited-state configuration should pave the way to control the stereochemical course of photoreaction due to the orbital approaches required for photochemical reactivity.