Preparation of Novel Selenopenams by Intramolecular Homolytic Substitution 英文参考文献.docVIP

Molecules 2004, 9, 466-471 molecules ISSN 1420-3049 Preparation of Novel Selenopenams by Intramolecular Homolytic Substitution Michael W. Carland and Carl H. Schiesser* School of Chemistry, Bio21 Molecular Science and Biotechnology Institute, The University of Melbourne, Victoria, Australia, 3010. Tel. (+61) 3-8344-4180, Fax (+61) 3-9347-5180. * Author to whom correspondence should be addressed; e-mail: carlhs@.au Received: 17 February 2004 / Accepted: 20 February 2004 / Published: 31 May 2004 Abstract: Photolyses of the thiohydroximate ester derivatives 13 and 21 of the 4- (benzyl-seleno)-2-azetidinoines 7 and 20, afford the 1-aza-7-oxo-4-selenabicyclo- [3.2.0]heptane ring systems 14 and 21 in good to moderate yield in processes that presumably involve intramolecular homolytic substitution at selenium with expulsion of benzyl radical. Extension of this methodology to the preparation of derivatives 24 of 12,2a-dihydro-1H,8H-azeto[2,1-b][1,3]benzoselenazin-1-one (22) is also described. Keywords: Free radical, homolytic substitution, selenium, β-lactam. Introduction Free-radical homolytic substitution chemistry is rapidly gaining acceptance as a versatile synthetic method [1]. Over the past few years, we have demonstrated the effectiveness of this chemistry for the preparation of selenium and tellurium-containing higher heterocycles. Indeed, so versatile is the free-radical approach that many classes of compound including some of hitherto unknown structure have been successfully prepared. Among these are included 5-deoxy-5-seleno pyranose sugars (eg. 1) [2], and novel selenium and tellurium analogues (eg. 2) [3] of the important antioxidant, α-tocopherol. It is generally appreciated that β-lactam based antibiotics have a limited future given increased resistance demonstrated by many strains of bacteria [4]. There is an urgent need for the developmen