53(P16) ヨウ化サマリウムの特性を利用した数種の天然物合成と新規反応系の開発(ポスター発表の部)

概要

論文の詳細を見る
Samarium (II) diiodide, originally introduced by Kagan and co-workers into organic synthesis, has been established as a useful synthetic reagent and a number of interesting reactions have been developed by application of this reagent. Recently we developed samarium (II) diiodide-promoted carbon-carbon bond cleavage reaction of γ-halo carbonyl compounds, and this fragmentation reaction was applied to the syntheses of (-)-invictolide, (+)-crobarbatic acid, and (+)-integerrinecic acid lactone. (-)-Invictolide was isolated from the red imported fire ant queens, Solenopsis invicta, as a queen recognition pheromone. (+)-Crobarbatic acid, and (+)-integerrinecic acid lactone is the necic acid components of 11- and 12-membered pyrrolizidine alkaloids, crobarbatine and integerrimine, respectively. As an extension of this fragmentation reaction for the synthesis of physiologically active compounds, we synthesized the side chains of petrosterol, isolated from Petrosia ficiformis, and aragusterols, isolated from the Okinawan sponge of the genus Xestospongia. Furthermore, the stereoselective synthesis of petrosterol utilizing SmI_2-promoted Barbier-type coupling reaction was achieved. During this work, we have found that TMSCl was effective additive for SmI_2-promoted reduction of ketones and for the pinacol coupling.
天然有機化合物討論会の論文
1997-07-20