38 ネオカルチノスタチンクロモフォア関連化合物の合成研究(口頭発表の部)

概要

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Neocarzinostatine chromophore (1), an active component of antitumor antibiotic neocarzinostatine produced by Strepromyces Carzinostsaticus, has been reported to possess novel bicyclo[7.3.0]dodecadienediyne system, which has been proposed to relate deeply with its biological activities. In our project aiming at the synthesis of stable but still active analogues of 1, we could develop a novel synthetic scheme toward the cyclic dienediyne system. Thus, palladium-catalyzed coupling reaction of (Z)-enol triflate (8) and optically active acetylenediol (22) prepared from D-xylose afforded dienediynediol (23) in a good yield. Tosylation and desilylative epoxide formation gave dienediyneepoxide (24). Upon treatment of 24 with lithium bistrimethylsilylamide in THF at ?-78℃ followed by boron trifluoride etherate complex, smooth cyclization was observed to produce 10-membered cyclic dienediyne (2), whose structure was confirmed by measuring the long-range coupling between C_6H-C_9H in the ^1H-NMR spectra of acetate (3). Attempt to obtain 9-membered cyclic analogue from either epoxide (27) or aldehyde (28) were unsuccessful.
天然有機化合物討論会の論文
1991-09-07