Stereoselective Transformation of Cyclodecene-1,4-dione Systems, Derived from Steroids, to the Corresponding spiro-γ-lactones. A Semiempirical MO Study 英文参考文献.docVIP

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Stereoselective Transformation of Cyclodecene-1,4-dione Systems, Derived from Steroids, to the Corresponding spiro-γ-lactones. A Semiempirical MO Study 英文参考文献.doc

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Molecules 1999, 4, 272-278 molecules ISSN 1420-3049 Stereoselective Transformation of Cyclodecene-1,4-dione Systems, Derived from Steroids, to the Corresponding spiro-g-lactones. A Semiempirical MO Study Ljubinka Lorenc1, Vladimir Pavlovich1, Ivan Juranich1*, Mihailo Lj. Mihailovich1, Lidija Bon- darenko-Gheorghiu2, Natalija Krstich2 and Milan Dabovich2 1 Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, Box 158, YU-11001 Belgrade, Yugoslavia Tel.: (+38111)-3281-867, Fax: (+38111)-3281-867, E-mail: ijuranic@chem.bg.ac.yu 2 Center for Chemistry, ICTM, P. O. Box 815, YU-11001 Belgrade, Yugoslavia *Author to whom correspondence should be addressed. Received: 21 June 1999 / Accepted: 20 July 1999 / Published: 12 September 1999 Abstract: The thermal and acid-catalyzed intramolecular rearrangement of the (Z)- and (E)- cyclodecene-1,4-dione compounds deriving from steroids, 2a,b and 3a,b, respectively, pro- ceeds stereoselectively to give the corresponding configurationally different spiro-g-lactone derivatives, the (5R,9R)-isomers 4a,b (from the (Z)-cyclodecenediones 2a,b) and the (5R,9S)-isomers 5a,b (from the (E)-cyclodecenediones 3a,b). The semiempirical MNDO- AM1 and PM3 molecular orbital methods were applied to elucidate the possible mechanistic pathway of the observed intramolecular process leading to the spiro-g-lactone structures. Keywords: seco-Steroids, Molecular rearrangement, Acid catalysis, AM1, PM3. Introduction Recently it was reported [1,2] that the stereoisomeric (Z)- and (E)-6,9-dioxocyclodec-3-enyl deriva- tives 2a,b and 3a,b, respectively (Scheme 1) (obtained by oxidative fragmentation of the C(5)- C(10) bond in 5-hydroxy-8-oxo-8,14-seco-5a -androstane-3b,17b-diyl diacetate (1a) (X=H2, R=OAc) [3,4], ? 1999 by the authors. Reproduction of this article, by any means, is permitted for noncommercial purposes. 273 Molecules 1999, 4 and 5-hydroxy-8,14-dioxo-8,14-seco-5a -cholestane-3b-yl acetate (1b