Stereoselective Transformation from Conjugated Alkynone to Nonconjugated (Z)-3-Iodo-3-alken-1-one. Its Mechanism Study and Application in Organic Synthesis

從共軛烴基炔酮到非共軛（順式）-3-碘-3-烴基烯-1-酮的高立體選擇性轉變。其反應機構及在有機合成上的研究

羅芬臺(Fen-Tair Luo)

《中央研究院化學研究所集刊》 45期 (1998/03) Pp. 15-26

https://doi.org/10.6522/BICAS.1998.45.2

摘要

共軛型的炔酮類化合物在碘化鈉，氯化三甲基矽及水，並以乙腈作溶劑下，可進行反應得到產率及立體選擇性均佳的非共軛型的（順式）－碘化烯酮類化合物。研究結果顯示3-癸炔-2-酮的反應是由先產生碘化氫進行炔基加成反應，得到（順式）-及（反式）-4-碘-3-癸烯-2-酮，再進行氯化三甲基矽催化的共軛化反應產生（順式）-4-碘-4-癸烯-2-酮。利用上述非共軛化反應，我們成功地開發一種利用碘化非共軛烯酮分子來合成α-位置上帶有順式的碳－碳雙鍵丁內酯化合物。此類化合物可用來調節植物生長的快慢。我們也利用鈀催化劑及有機鋅化合物對（順式）-4-碘-4-癸烯-2-酮進行耦合反應生產具有三取代基的烯類化合物。

並列摘要

Treatment of conjugated alkynone with sodium iodide, chlorotrimethylsilane, and water in acetonitrile gave deconjugated (Z)-3 -iodo-3-alken-1-one in good yield and with high stereoselectivity (≥ 95%). Mechanistic study showed that hydrogen iodide, generated from sodium iodide, chlorotrimethylsilane and water, underwent regioselective addition to the conjugated ynone, e.g. 3-decyn-2-one, to form conjugated (E)-4-iodo-3-decen-2- one and (Z)-4-iodo-3-decen-2-one. Then, chlorotrimethylsilane catalyzed the deconjugation reaction to form deconjugated (Z)-4-iodo-4-decen-2-one. The application of the above deconjugation reaction was demonstrated by the stereoselective synthesis of (Z)-α-alkylidene-y-butyrolactone, a plant growth regulator, and the palladium-catalyzed cross coupling reactions of (Z)-4-iodo-4-decen-2 -one with organozinc chlorides.