The mechanism of the first step of the Mitsunobu reaction

Autor:	David Brian Camp, Ian D. Jenkins, Mark von Itzstein
Rok vydání:	2015
Předmět:	Stereochemistry Organic Chemistry Biochemistry Phosphorane Cycloaddition chemistry.chemical_compound Betaine chemistry Nucleophile Drug Discovery Michael reaction Physical organic chemistry Mitsunobu reaction Phosphine
Zdroj:	Tetrahedron. 71:4946-4948
ISSN:	0040-4020
DOI:	10.1016/j.tet.2015.05.099
Popis:	Previous DFT calculations employing phosphine (PH 3 ) and dimethyl azodicarboxylate showed that a cyclic O , N -phosphorane was energetically favored relative to betaine formation. In this study strong experimental support for the formation of the phosphorane is described. The question of whether betaine formation occurs via nucleophilic attack of the phosphine on the azodicarboxylate as has been previously assumed, or via a [4+2] cycloaddition (cheletropic) reaction to give the O , N -phosphorane, followed by ring-opening to give the betaine has not been resolved. An answer to this intriguing question is provided.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::55378d9e17ccbe0d37937bf81cdfc704 https://doi.org/10.1016/j.tet.2015.05.099 Zobrazit plný text záznamu Full Text from ScienceDirect