Chemical- and light-induced isomerization of the P=C bond of a 1-phosphabutadiene

Autor:	Henry T G Walsgrove, Philipp Dabringhaus, Derek P. Gates, Brian O. Patrick
Rok vydání:	2020
Předmět:	chemistry.chemical_compound chemistry Photoisomerization Phosphorus Organic Chemistry Light induced Phosphaalkene chemistry.chemical_element General Chemistry Medicinal chemistry Isomerization Catalysis
Zdroj:	Canadian Journal of Chemistry. 98:373-378
ISSN:	1480-3291 0008-4042
Popis:	Treatment of Mes*P=C(Si(CH3)3)Br with CH2=CHMgBr in the presence of Pd(0) affords 1-phosphabutadiene Mes*P=C(Si(CH3)3)–CH=CH2 (1) selectively as the Z isomer. Remarkably, treatment of Z-1 with n-BuLi (0.1 equiv.) resulted in quantitative formation of E-1. The exact role of the n-BuLi is unknown; however, it appears to be required to promote the isomerization in the absence of light. The isomerization of Z-1 to E-1 was also mediated by sunlight with the reaction mixture consisting of a ca. 1:9 ratio of Z-1 to E-1. DFT calculations were consistent with the thermodynamic favorability of the isomerization of Z-1 to E-1.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::9e2db2a604595c0f43fbfec982cc4339 https://doi.org/10.1139/cjc-2020-0055 Zobrazit plný text záznamu Plný text ve formátu PDF