Generation of Iminophosphoranes and Phosphorus Ylides from (Alkylamino) phosphonium Salts and their Reactions with Isocyanates. Mechanism Elucidation by the DFT Method

Autor:	Fumio Ando, Akimasa Takeuchi, Yuichi Okazaki, Jugo Koketsu
Rok vydání:	2006
Předmět:	Phosphine oxide chemistry.chemical_classification Phosphorus Phosphonium salt chemistry.chemical_element Electrochemistry Medicinal chemistry chemistry.chemical_compound chemistry Ylide Organic chemistry Phosphonium Phenylisocyanate Carbodiimide
Zdroj:	Electrochemistry. 74:758-767
ISSN:	2186-2451 1344-3542
Popis:	Electrochemical reduction of substituted (alkylamino)phosphonium salts under the presence of phenylisocyanate was carried out to confirm the generation of iminophosphoranes and phosphorus ylides. The reactions of the generated iminophosphorane with phenylisocyanate gave a phosphine oxide and a carbodiimide as the products of the Aza-Wittig-type reactions. When the ylide generation is favorable, the generated phosphorus ylide reacted with phenylisocyanate to give the intermediate betaines as the result of Wittig-type reaction and succeeding H-shift leads to more stable phosphorus ylides. To elucidate the mechanisms of selective synthesis of the iminophosphoranes and phosphorus ylides from a single (alkylamino)phosphonium salt, the theoretical density functional calculations were performed by using B3LYP with the 6–31+G(d) basis set.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::8245a88f0052bd1d32e0b3e2c1f7fb9d https://doi.org/10.5796/electrochemistry.74.758 Zobrazit plný text záznamu