ChemInform Abstract: SET-Induced Photorearrangement of 2-Phenylallyl Phosphites. Stereochemistry at Phosphorus. Application to Cyclic Nucleotide Derivatives

Autor:	Alan E. Sopchik, Wesley G. Bentrude, David C. Hager
Rok vydání:	2010
Předmět:	Cation radical Diradical Chemistry Stereochemistry Phosphorus Diastereomer chemistry.chemical_element General Medicine Phosphonate law.invention Cyclic nucleotide chemistry.chemical_compound law Walden inversion Bond cleavage
Zdroj:	ChemInform. 31
ISSN:	1522-2667 0931-7597
DOI:	10.1002/chin.200033168
Popis:	The stereochemistry at phosphorus of the SET-induced photorearrangement of diastereomeric 4-tert-butyl-2-phenylallyl-1,3,2-dioxaphosphorinanes (8) to the corresponding 2-phenylallylphosphonates (9), which involves excited singlet 1,4-dicyanonaphthalene (1DCN*) as one-electron oxidant, was investigated. The rearrangement occurs with close to complete retention of configuration at phosphorus. The previously postulated mechanism for this photorearrangement is shown to be consistent with the stereochemical finding. Thus, one-electron reduction by DCN.- of the presumably stereospecifically formed distonic cyclic 1,3-cation radical intermediate 15, generated from cis-8 (Scheme 2), yields the thermodynamically stable diradical 16. β scission of 16 forms phosphonate cis-9. An alternative mechanism involving β scission of 15 to a styryl cation radical, prior to one-electron reduction to 15, is discounted on the basis of unpublished trapping studies using MeOH. The direct, kinetically controlled formation of diradi...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::1b05c2f87e05e041b5b75ab8cd115e77 https://doi.org/10.1002/chin.200033168 Zobrazit plný text záznamu Plný text