Triplet-Sensitized Photorearrangements of 2-Phenylallyl Phosphites

Autor:	Michael Tabet, Joel M. Harris, Yuh Wern Wu, Srinivasan Ganapathy, S.-G. Lee, R. Thomas Cambron, Kevin P. Dockery, Wesley G. Bentrude
Rok vydání:	1996
Předmět:	Phosphorus chemistry.chemical_element Regioselectivity Triphenylene General Chemistry Ring (chemistry) Biochemistry Medicinal chemistry Phosphonate Catalysis chemistry.chemical_compound Colloid and Surface Chemistry chemistry Benzene Acetonitrile Bond cleavage
Zdroj:	Journal of the American Chemical Society. 118:6192-6201
ISSN:	1520-5126 0002-7863
Popis:	The triplet-sensitized photorearrangements of 2-phenylallyl phosphites 1, 3, and 4 to the corresponding 2-phenylallylphosphonates 1a, 3a, and 4a are shown to proceed with complete regioselectivity (5 → 6 and Scheme 1). A mechanism is proposed in which the 1,2-biradical-like styryl triplet, 9, adds oxidatively to three-coordinate phosphorus to generate a cyclic, triplet, phosphoranyl 1,3-biradical, 10, that undergoes rapid subsequent β scission to generate product 2−phenylallylphosphonate, 11. Phosphonate 1a is formed near-quantitatively from dimethyl 2-phenylallyl phosphite, 1. Phosphites 2−4, with phosphorus contained in a five-, six-, or seven-membered ring, respectively, photorearrange much more slowly, although yields of phosphonates 3a and 4a of 50−70% are generated. Quantum yields for the formation of phosphonates 1a, 3a, and 4a, on sensitization by triplet triphenylene, were determined to be 0.25, 0.003, and 0.005, respectively, in benzene. Similar values were found in acetonitrile and benzene usin...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::39ca8b5cbeba1d59a047b54bd0070f6e https://doi.org/10.1021/ja960428r Zobrazit plný text záznamu