Boronic acids: New coupling partners in room-temperature suzuki reactions of alkyl bromides. Crystallographic characterization of an oxidative-addition adduct generated under remarkably mild conditions
Boronic acids: New coupling partners in room-temperature suzuki reactions of alkyl bromides. Crystallographic characterization of an oxidative-addition adduct generated under remarkably mild conditions
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DOI：
10.1021/ja0283899
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发表时间：
2002-11-20
影响因子：
15
通讯作者：
Fu, GC
中科院分区：
文献类型：
--
作者：
Kirchhoff, JH;Netherton, MR;Fu, GC
Suzuki反应是一种非常有用的交叉偶联过程，已广泛应用于合成化学中，而硼酸是迄今为止最常用的偶联配偶体。然而，迄今为止，还没有开发出将硼酸与未活化的烷基（与芳基或乙烯基相反）亲电试剂交叉偶联的通用方法。本报告描述了在室温下实现该目的的催化剂体系。在机理方面，该研究表明Pd（P（t-Bu）2 Me）2在令人惊讶的温和条件（0 °C）下经历氧化加成。所得加合物对β-氢化物消除足够稳定，可以对其进行结构表征，并且它是交叉偶联过程中的化学活性中间体。
The Suzuki reaction is an exceptionally useful cross-coupling process that has been widely applied in synthetic chemistry, and boronic acids are, by far, the most commonly employed coupling partner. To date, however, no versatile method has been developed for cross-coupling boronic acids with unactivated alkyl (as opposed to aryl or vinyl) electrophiles. This report describes a catalyst system that achieves this objective at room temperature. On the mechanistic side, this study demonstrates that Pd(P(t-Bu)2Me)2undergoes oxidative addition under surprisingly mild conditions (0 °C). The resulting adduct is sufficiently stable toward β-hydride elimination that it can be structurally characterized, and it is a chemically competent intermediate in the cross-coupling process.