A Computational Study on the Photochemical O-HFunctionalization of Alcohols with Diazoacetates

In this computational study, we provide a detailedanalysis of the underlying reaction mechanism and show that asinglet carbene is initially formed. Depending on the pKAof thealcohol, this singlet carbene can engage in direct protonation orenol formation to yield the O-H functionalization product. On thecontrary, propargylic alcohols take up a dual role and form acomplex with the carbene intermediate that leads to facilecyclopropenation reactions.

Automated summary

In this computational study, the authors analyze the reaction mechanism and observe the formation of a singlet carbene. Depending on the pKa value of the alcohol, this carbene can undergo direct protonation or enol formation to yield different products. Propargylic alcohols, on the other hand, form a complex with the carbene intermediate, leading to facile cyclopropenation reactions.