Wang Chao, Xu Zhaoqing, Tobrman Tomas, Negishi Ei-Ichi
Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Dr., West Lafayette, IN 47907-2084, USA.
Adv Synth Catal. 2010 Mar 8;352(4):627-631. doi: 10.1002/adsc.200900766.
The hitherto unprecedented palladium-catalyzed cross-coupling of ()-β-bromo-β-arylethenylboranes can be made to proceed satisfactorily through (1) the use of highly catalytically active bis(tri--butylphosphine)palladium or dichloro,-bis-(2,6-diisopropylphenyl)imidazol-2-ylpalladium and (2) conversion of dibromoboryl group to (pinacol)boryl group. Thus, a wide variety of carbon groups can be used to substitute bromine in ≥98% stereo- and regioselectivity, while suppressing the otherwise dominant β-debromoboration. Together with the alkylethyne-based protocols, the alkyne bromoboration-Negishi coupling tandem process has emerged as the most widely applicable and highly selective route to trisubstituted alkenes including those that are otherwise difficult to access.
通过（1）使用高催化活性的双（三叔丁基膦）钯或二氯[，-双-（2,6-二异丙基苯基）咪唑-2-基]（-氯吡啶）钯，以及（2）将二溴硼基转化为（频哪醇）硼基，可以使前所未有的（）-β-溴-β-芳基乙烯基硼烷的钯催化交叉偶联反应顺利进行。因此，可以使用各种各样的碳基团以≥98%的立体和区域选择性取代溴，同时抑制原本占主导的β-脱溴硼化反应。与基于烷基乙炔的方法一起，炔基溴硼化-根岸偶联串联过程已成为制备三取代烯烃最广泛适用且高度选择性的路线，包括那些难以通过其他方法获得的烯烃。
