Regio- and chemoselectivity in S- and O- difluoromethylation reactions using diethyl (bromodifluoromethyl)phosphonate

Autor:	Lea Yehezkel, Yossi Zafrani, Daniele Marciano, Gil Fridkin, Orit Redy-Keisar, Iris Binyamin, Eytan Gershonov, Eyal Drug, Dafna Amir
Rok vydání:	2021
Předmět:	Difluorocarbene Chemistry Organic Chemistry Regioselectivity Biochemistry Medicinal chemistry Phosphonate Inorganic Chemistry Hydrolysis chemistry.chemical_compound Nucleophile Environmental Chemistry Physical and Theoretical Chemistry Chemoselectivity
Zdroj:	Journal of Fluorine Chemistry. 250:109867
ISSN:	0022-1139
DOI:	10.1016/j.jfluchem.2021.109867
Popis:	The effective difluoromethylations of various S- and O- based- nucleophiles, presenting a wide range of pKa values, using diethyl(bromodifluoromethyl) phosphonate (1) under basic conditions is described. These reactions, which rely on the quantitative generation of difluorocarbene formed through the hydrolysis of 1, were found to be effective only once the starting materials had pKa values of less than ca. 11. Importantly, in cases in which the substrates held two or three nucleophilic centers this feature was successfully implemented to achieve a high chemo- or regioselective difluoromethylation of the center exhibiting the lowest pKa value and the highest polarizability.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::85df558034b04b2af36efc9e47fd491b https://doi.org/10.1016/j.jfluchem.2021.109867 Zobrazit plný text záznamu Full Text from ScienceDirect