regio- and stereoselective [2+2] photodimerization of 3-substituted 2-alkoxy-2-oxo-2h-1,2-benzoxaphosphorines区和立体选择[2 + 2]光二聚3-substituted 2-alkoxy-2-oxo-2h-1,2-benzoxaphosphorines.pdfVIP

Molecules 2002, 7, 420-432 molecules ISSN 1420-3049 Regio- and Stereoselective [2+2] Photodimerization of 3- Substituted 2-Alkoxy-2-oxo-2H-1,2-benzoxaphosphorines Rositca D. Nikolova, G. N. Vayssilov, Nestor Rodios* and Anka Bojilova 1 Department of Organic Chemistry, University of Sofia, Y. Bourchier av. 1, Sofia, 1126, Bulgaria. e-mail: abojilova@chem.uni-sofia.bg 2 Laboratory of Organic Chemistry, Chemistry Department, University of Thessaloniki, Thessaloniki 540006, Greece. * To whom correspondence should be addressed; e-mail: rodios@chem.auth.gr Received: 10 July 2001; in revised form: 10 April 2002 / Accepted: 12 April 2002 / Published: 31 May 2002 Abstract: Diethyl 1,2-benzoxaphosphorine-3-carboxylates 5 undergo a regio- and stereoselective [2+2] photodimerization reaction in methanol solution under the action of sunlight, giving in all cases the corresponding anti head-to-tail dimers 6 and 7. Concerning the stereogenic P atom, the photodimerization is also stereoselective, and the centrosymmetric stereoisomer 6 predominates over the non symmetric P-epimer 7. Keywords: 2-Oxo-2-alkoxy-1,2-benzoxaphosphorines, [2+2]photocycloaddition, benzoxaphphorine dimers Introduction The photochemical [2+2] dimerization of 2-oxo-2H-1-benzopyrans (coumarins) is well known [1- 7]. Over the last few years there has been a growing interest in some coumarin photodimers due to their applications in organic synthesis [8-10], in medicine [11-13] and in other modern technologies [14-16]. All four possible regio and stereoisomers, i.e. syn head-to-he