P-76 ヘテロ共役付加と不斉転写型シグマトロピー転位を利用した鎖状二級アルキルエーテル合成とその応用(ポスター発表の部)

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Stereoselective construction of medium-sized cyclic ethers is one of the major problems in the synthesis of fused-polycyclic ether natural compounds, represented by ciguatoxin CTX3C. We have explored efficient solutions for the problem, and examined an application of a ring-closing olefin metathesis reaction (RCM), one of the most reliable methods for the formation of medium-ring structure, to cyclic ether synthesis. Although preparation of the precursors for RCM involved a serious difficulty in the stereoselective construction of their acyclic di-sec-alkyl ether part, we found its effective answers, namely, the [2,3]-Wittig rearrangement of a 3-alkoxyallyloxyacetic acid ester and the Ireland-Claisen rearrangement of a 3-alkoxyallyl glycolate. These rearrangement reactions stereoselectively produced 1,2-dialkoxy structures, which were easily transformed to medium cyclic ethers through a process including RCM. Details of the rearrangement reactions and the preparation method for the substrates using a hetero-conjugate addition reaction will be discussed at the presentation. The applications of these rearrangement reactions to the synthesis of the EF-ring of CTX3C will also be described.
天然有機化合物討論会の論文
2007-08-24