DFT Case Study of the Mechanism of a Metal-Free Oxygen Atom Insertion into a p-Quinone Methide C(sp3)–C(sp2) Bond

Autor:	Travis Dudding, Thomas Lectka, Muhammad Kazim, Ivor Smajlagic
Rok vydání:	2020
Předmět:	chemistry.chemical_compound Oxygen atom Chemistry Computational chemistry Mechanism (philosophy) Unique element Organic Chemistry Molecule Reactivity (chemistry) Quinone methide Chemical space
Zdroj:	The Journal of Organic Chemistry. 85:10110-10117
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.0c01371
Popis:	The site-selective introduction of an oxygen atom into an organic molecule, without the assistance of metals, is a useful transformation, though understanding the mechanistic underpinning of such a process is oftentimes a challenging task. In exploring this chemical space and in building upon experimental precedents, we have utilized computational tools to delineate the mechanistic details of site-selective oxygen atom insertion into a p-quinone methide C(sp3)-C(sp2) bond. To this end, several different reaction pathways for oxygen atom insertion were explored-each encompassing a unique element qualifying the respective pathway as being more or less feasible. The findings of these investigations revealed several features that were vital to this reactivity, including the formation of a dimeric intermediate, interconversion between ground- and excited-state species, and strain. Notably, the latter finding adds to the portfolio of strain-release-driven reactions that have emerged as popular methods to achieve otherwise difficult chemical transformations.
Databáze:	OpenAIRE
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