Sequential cross-coupling of 1,4-bissilylbutadienes: Synthesis of unsymmetrical 1,4-disubstituted 1,3-butadienes
Sequential cross-coupling of 1,4-bissilylbutadienes: Synthesis of unsymmetrical 1,4-disubstituted 1,3-butadienes
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DOI：
10.1021/ja0518373
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发表时间：
2005-06-08
影响因子：
15
通讯作者：
Tymonko, SA
中科院分区：
文献类型：
--
作者：
Denmark, SE;Tymonko, SA
完成了不对称的1,4-二硅基-1,3-丁二烯的温和、一般和立体定向交叉偶联反应。通过在二烯基硅醇的一端使用苯基二甲基硅基或2-噻基二甲基硅基单元，可以在轻度碱性条件下（KOTMS）进行选择性交叉偶联，为广泛的芳基和烯基偶联伙伴提供产率高的4-芳基-1,3-二烯基硅烷。TBAF与富电子卤化物或贫电子卤化物的作用可明显地实现二次交叉耦合。连续的过程可以压缩成一个“一锅”过程，总的来说，不对称的1,4-二烷基-1,3-丁二烯的收率很高。
A mild and general and stereospecific cross-coupling reaction of unsymmetrical 1,4-bissilyl-1,3-butadienes has been accomplished. By the use of either a benzyldimethylsilyl or 2-thienyldimethylsilyl unit at one end of the dienylsilanol, a selective cross-coupling could be effected under mildly basic conditions (KOTMS) to afford 4-aryl-1,3-dienylsilanes in excellent yield for a wide range of aryl and alkenyl coupling partners. The second cross-coupling could be effected cleanly by the action of TBAF with electron-rich or electron-poor halides. The sequential process could be telescoped into a “one pot” procedure with overall excellent yields of the unsymmetrical 1,4-diaryl-1,3-butadienes.