Organocatalytic C–H hydroxylation with Oxone®enabled by an aqueous fluoroalcohol solvent system

Autor:	Ashley M. Adams, J. Du Bois
Rok vydání:	2014
Předmět:	Solvent Hydroxylation chemistry.chemical_classification Solvent system chemistry.chemical_compound Hydrocarbon Aqueous solution chemistry Organic chemistry General Chemistry Selectivity Oxaziridine Catalysis
Zdroj:	Chem. Sci.. 5:656-659
ISSN:	2041-6539 2041-6520
DOI:	10.1039/c3sc52649f
Popis:	Selective hydroxylation of 3° and benzylic C–H bonds is made possible using a non-metal-based catalyst system, Oxone as the terminal oxidant, and an aqueous fluoroalcohol solvent mixture. The choice of solvent is uniquely effective for this process, but seemingly at odds with our finding that H2O promotes reduction of the oxaziridine intermediate. Our studies suggest that the hydroxylation reaction is occurring within a fluoroalcohol microdroplet, which both concentrates the reactants and mitigates the deleterious impact of H2O on oxaziridine stability. These discoveries have led to demonstrable improvements in the organocatalytic oxygenation of hydrocarbon substrates and, for the first time, the successful use of Oxone with this catalyst system. Reactions generally afford product and unreacted starting material in near quantitative amounts and display outstanding selectivity for 3° and benzylic C–H bond oxidation.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::42d2446fdaadda31d9835bd457b6d631 https://doi.org/10.1039/c3sc52649f Zobrazit plný text záznamu