Silaboration of [1.1.1]Propellane: A Storable Feedstock for Bicyclo[1.1.1]pentane Derivatives
Silaboration of [1.1.1]Propellane: A Storable Feedstock for Bicyclo[1.1.1]pentane Derivatives
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DOI：
10.1002/anie.201909655
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发表时间：
2019-11-08
影响因子：
16.6
通讯作者：
Uchiyama, Masanobu
中科院分区：
文献类型：
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作者：
Kondo, Masaki;Kanazawa, Junichiro;Uchiyama, Masanobu
[1.1.1]螺旋烷的硅硼化使B和Si官能团直接引入到双环[1.1.1]戊烷(BCP)支架上，在温和的、无添加剂的条件下，产率很高。硅硼化的BCP无需柱层析纯化，可一步得到克级规模的BCP，且易于储存和处理，为BCP衍生物提供了一种多功能的合成中间体。我们还描述了BCP支架上C-B/C-Si键的各种转化，包括使用高活性BCP硼酸酯、铜(I)氧化物和PdCl2(Dppf)催化体系在BCP骨架的高度空间受阻的桥头sp(3)碳中心发展了改进的Suzuki-Miyaura交叉偶联反应。
The silaboration of [1.1.1]propellane enables direct introduction of B and Si functional groups onto the bicyclo[1.1.1]pentane (BCP) scaffold in high yield under mild, additive-free conditions. The silaborated BCP can be obtained on a gram-scale in a single step without the need for column-chromatographic purification, and is storable and easy to handle, providing a versatile synthetic intermediate for BCP derivatives. We also describe various conversions of the C-B/C-Si bonds on the BCP scaffold, including development of a modified Suzuki-Miyaura cross-coupling reaction at the highly sterically hindered bridgehead sp(3) carbon center of the BCP skeleton using a combination of highly activated BCP boronic esters, copper(I) oxide, and a PdCl2(dppf) catalyst system.