PALLADIUM-CATALYZED CARBONYLATIVE COUPLING OF VINYL TRIFLATES WITH ORGANOSTANNANES - A TOTAL SYNTHESIS OF (+/-)DELTA-9(12)-CAPNELLENE
PALLADIUM-CATALYZED CARBONYLATIVE COUPLING OF VINYL TRIFLATES WITH ORGANOSTANNANES - A TOTAL SYNTHESIS OF (+/-)DELTA-9(12)-CAPNELLENE
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DOI：
10.1021/ja00336a033
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发表时间：
1984-01-01
影响因子：
15
通讯作者：
STILLE, JK
中科院分区：
文献类型：
--
作者：
CRISP, GT;SCOTT, WJ;STILLE, JK
钯催化的三氟甲磺酸乙烯酯与烷基-、乙烯基-、烯丙基-和芳基锡烷的羰基化偶联给出了良好的交叉偶联酮产物产率。区域选择性形成的乙烯基三氟甲磺酸酯可用于生产二乙烯基酮作为区域异构纯的化合物。乙烯基锡烷的E和Z几何形状在偶联反应期间保持。二乙烯基酮是重要的有机合成中间体，它可以作为Michael受体与多种亲核试剂反应，也可以参与Nazarov反应生成环戊烯酮。2我们最近报道了钯催化的乙烯基碘与乙烯基锡烷的羰基化偶联以良好的产率得到不对称的二乙烯基酮（等式1）。3
The palladium-catalyzed carbonylative coupling of vinyl triflates with alkyl-, vinyl-, allyl-, and arylstannanes gives good yields of the cross-coupled ketone products. Regioselectively formed vinyl triflates can be usedto produce divinyl ketones as regioisomerically pure compounds. The E and Z geometry of the vinylstannane is maintained during the coupling reaction. This methodology was applied to a total synthesis of the marine natural product A9< 12)-capnellene.Divinyl ketones are important intermediates in organicsynthesis since they can act as Michael acceptors for a diverse range of nucleophiles' or participate in Nazarov reactions to give cyclo-pentenones. 2 We reported recently that the palladium-catalyzed carbonylative coupling of vinyl ioides with vinylstannanes afforded unsymmetrical divinyl ketones in good yields (eq l). 3