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Updated: Sep 24, 2025
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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions
Published on: July 17, 2020
A Computational Study on the Photochemical O-H Functionalization of Alcohols with Diazoacetates
1RWTH Aachen University, Institute of Organic Chemistry, Landoltweg 1, D-52074 Aachen, Germany.
Abstract:
In this computational study, we provide a detailed analysis of the underlying reaction mechanism and show that a singlet carbene is initially formed. Depending on the pKA of the alcohol, this singlet carbene can engage in direct protonation or enol formation to yield the O-H functionalization product. On the contrary, propargylic alcohols take up a dual role and form a complex with the carbene intermediate that leads to facile cyclopropenation reactions.
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