121(P-58) エキソメチレン化合物の分子内Pauson-Khand反応とリコポジウムアルカロイド、magellanine合成への応用(ポスター発表の部)
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概要
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Pauson-Khand reaction is well known to be a useful reaction for formation of cyclopentenones from alkyne-cobalt complex with alkenes and much attention has been focused on both its inter- and intra-molecular reactions. For the intramolecular cyclic reaction, there are many reports on the reaction of endo-cyclic enynes having alkynyl group on olefinic moiety to give angular tricyclic compounds. However, only a few reports on the reaction of exo-cyclic enynes. We conducted intramolecular Pauson-Khand reaction of various exo-cyclic enynes to give angular type 6-5-5 and 5-5-5 tricyclic compounds in good to high yield. In particular, the present reaction offers convenient preparation of tricyclic compounds having contiguous quaternary centers, which could not be synthesized in practical yield by the reaction of endo-cyclic olefins, because with endo-cyclic olefins the reaction of highly hindered tetra-substituted cyclic enynes should be required. Next, as application of the present reaction a total synthesis of Lycopodium alkaloid, magellanine (31). which has a unique tetracyclic structure, was investigated. Thus, hydroxymethylcyclohexenone (32) was converted to various siloxy allylacetates (35a-c), Ireland-Claisen rearrangement of which was examined. Among them, TIPS ether (35a) resulted in the best trans selectivity to give 36a along with cis isomer (36b) (ca. 10:1 ratio). Since Pauson-Khand reaction of 36a was unsuccessful, desilylated exo-cyclic enyne (41) was prepared from 36a in several steps. The reaction of 41 proceed successfully to give angular tricyclic products (42), which is a basic skeleton in magellanine. Transformation of 42 to magellanine (31) is now in progress.
- 天然有機化合物討論会の論文
- 2000-10-01
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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岩原 主彦
東京理大薬
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