Further Mechanistic Investigations into the Blue Light-Driven O–H Functionalization of Alcohols by Aryldiazoacetates
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide The blue light-driven O–H functionalization of alcohols by aryldiazoacetates represents a modern synthetic application of diazo photochemistry. Previous work by us and the Koenigs group demonstrated that this chemistry occurs through a free singlet carbene intermediate generated from the photolysis of the aryldiazoacetate. However, there is significant controversy in the literature concerning the exact photochemical pathway through which the photolysis of aryldiazoacetates occurs, with at least three proposed mechanisms in the literature. One group argued that photolysis requires protonation of the carbonyl to occur, another group described the C–N bond-breaking occurring on T 1 after intersystem crossing from S 1, and a third group argued that the singlet carbene is generated on S 0 after internal conversion from S 1 . Additionally, no mechanistic explanation exists in the literature for the dependence of the O–H functionalized product yield on the chemical structure of the aryldiazoacetate. In this paper, we apply high-level quantum chemical methods to develop a refined picture of aryldiazoacetate photolysis and to build a mechanistic explanation for what controls the O–H functionalized product yield. Overall, our work provides new insights into an important chemical transformation initiated by the absorption of visible light.
Source: The Journal of Organic Chemistry
Institution: California State University, Fullerton
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Award: G3161234870
OpenAlex ID: W4411141080