Total Synthesis of (-)-(7S,10R)-Calamenene and (-)-(7S,10R)-2-Hydroxycalamenene by Use of a Ring-Closing Metathesis Reaction. A Comparison of the cis- and trans-Isomers 英文参考文献.docVIP

Molecules 2002, 7, 517-527 molecules ISSN 1420-3049 Total Synthesis of (-)-(7S,10R)-Calamenene and (-)-(7S,10R)- 2-Hydroxycalamenene by Use of a Ring-Closing Metathesis Reaction. A Comparison of the cis- and trans-Isomers Katsuyuki Nakashima, Masashi Imoto, Masakazu Sono, Motoo Tori,* Fumihiro Nagashima and Yoshinori Asakawa. Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima, 770-8514, Japan. Tel (+81) 88 622-9611, Fax (+81) 88 655-3051, homepage; http://p.bunri-u.ac.jp/~tori/english/e-tori.html * Author to whom correspondence should be addressed; e-mail: tori@ph.bunri-u.ac.jp Received: 2 May 2002; in revised form: 1 July 2002 / Accepted: 8 July 2002 / Published: 31 July 2002 Abstract: The title compounds have been synthesized starting from l-menthone by application of a ring-closing metathesis reaction to confirm their reported absolute and relative stereochemistry. Comparisons of the NMR spectra and specific rotations are also discussed. Keywords: Calamenene, hydroxycalamenene, ring closing metathesis, absolute configuration, sesquiterpene. Introduction The absolute configurations of both (7S,10R)-calamenene (1), isolated from Chamaecyparis nootkatensis by Andersen et al. [1] and (+)-2-hydroxycalamenene (2) [2], isolated from Dysoxylum acutangulum by Nishizawa et al. [3] were determined using CD spectra or X-ray analysis and chemical transformations. The stereochemistry of 1 was later revised after X-ray analysis [4]. We have been working on natural products found in the liverwort [5, 6] and have reported the isolation of several calamenenes [7, 8], including 5-hydroxycalamenene, whose structure was determined by X-ray analysis [8]. Up to now, total syntheses of these chiral substances have never been clearly reported because the final products were always a mixture of cis- and trans-isomers [9]. We are currently working on the  Molecules 200