Kong Wei, Che Chao, Wu Jialin, Ma Liai, Zhu Gangguo
Department of Chemistry, Zhejiang Normal University , 688 Yingbin Road, Jinhua 321004, China.
J Org Chem. 2014 Jun 20;79(12):5799-805. doi: 10.1021/jo500925p. Epub 2014 Jun 11.
An efficient Pd-catalyzed addition of boronic acids to silylacetylenes is described, providing β,β-disubstituted (E)- or (Z)-alkenylsilanes in satisfactory yields with excellent regio- and stereoselectivity under mild reaction conditions. It represents the first highly regio- and stereoselective addition of boronic acids to aryl and alkenyl silylacetylenes. Moreover, the sequential Pd-catalyzed boron addition/N-halosuccinimide-mediated halodesilylation reaction results in a stereodivergent approach to β,β-disubstituted alkenyl halides, which can serve as versatile synthetic intermediates for the stereodivergent assembly of (E)- and (Z)-trisubstituted alkenes via transition-metal-catalyzed cross-coupling reactions.
描述了一种高效的钯催化硼酸与硅基乙炔的加成反应，在温和的反应条件下，以令人满意的产率提供具有优异区域和立体选择性的β,β-二取代（E）-或（Z）-链烯基硅烷。这是硼酸首次对芳基和烯基硅基乙炔进行高度区域和立体选择性加成。此外，钯催化的硼加成/ N-卤代琥珀酰亚胺介导的卤代脱硅反应序列产生了一种立体发散的方法来合成β,β-二取代的烯基卤化物，其可作为通过过渡金属催化的交叉偶联反应进行（E）-和（Z）-三取代烯烃立体发散组装的通用合成中间体。
