86(P-20) リコポジウムアルカロイド、magellanineの合成研究(ポスター発表の部)
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概要
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Magellanine (1), which belongs to Lycopodium alkaloids, was isolated and characterized by MacLean and co-workers. Magellanine possesses unique tetracyclic skeleton, which is constituted by angular tricyclic framework with piperidine ring. Due to its interesting structural characteristics, magellanine lends itself as a challenging synthetic target and several synthetic approaches have been reported. We recently reported intramolecular Pauson-Khand reaction of various exo-cyclic enynes to give angular tricyclic compounds. Thus, total synthesis of magellanine could be achieved by application of this methodology via angular type 6-5-5 tricyclic compound. At first, hydroxymethylcyclohexenone (3) was converted in three steps to triisopropylsiloxyallyl acetate (5), Ireland-Claisen rearrangement of which and reduction with LiAlH_4 furnished trans-alcohol (6) as a single diastereomer. Dess-Martin oxidation of 6 followed by the reaction with t-butyl butynylcarbamate lead to exo-cyclic enynes (8a,b). Intramolecular Pauson-Khand reaction of 8a,b successfully gave rise to angular tricyclic compounds (9a,b). Reduction of enone (9a) afforded 10, which was transformed to MOM ether (11). Olefination of ketone (11) with Tebbe reagent gave exo-methylene compound (13), hydroboration-oxidation of which afforded alcohols. After separation of diastereomers via benzoyl ester (14a,b), mesylation of desired isomer (15) and subsequent cyclization promoted with t-BuOK furnished tetracyclic compounds (16). Reduction of 16 with LiAlH_4 and deprotection with hydrochloric acid afforded diol (17) in high yield. Conversion of 17 to magellanine (1a) is now under way.
- 天然有機化合物討論会の論文
- 2002-09-01
著者
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星野 修
東京理科大学薬学部
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石崎 幸
東京理科大学薬学部
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星野 修
Faculty Of Pharmaceutical Sciences Science University Of Tokyo
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石崎 幸
東京理大薬
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新見 由佳
東京理大薬
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星野 修
東京理大薬
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