Multifunctional P-ligand-controlled "silicon-centered" selectivity in Rh/Cu-catalyzed Si-C bond cleavage of silacyclobutanes
Multifunctional P-ligand-controlled "silicon-centered" selectivity in Rh/Cu-catalyzed Si-C bond cleavage of silacyclobutanes
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Rh/Cu 催化硅杂环丁烷 Si-C 键断裂中多功能 P-配体控制的“硅中心”选择性
DOI：
10.1039/d1qo01386f
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发表时间：
2021
影响因子：
5.4
通讯作者：
Xu Li-Wen
中科院分区：
文献类型：
--
作者：
Wang Xu;Huang Shuai-Shuai;Zhang Feng-Jiao;Xie Jia-Le;Li Zhao;Xu Zheng;Ye Fei;Xu Li-Wen
硅/碳转换策略，又称硅替代，在药物发现和材料科学中扮演着重要的角色。然而，目前还缺乏在复杂分子上引入硅中心的有效且精确控制的方法，这限制了含硅类药物分子的发展。在这里，我们揭示了一种史无前例的合成六元功能硅环的方法，该方法基于多官能膦促进的双金属Rh/Cu催化的Si-C键活化。相应的(4+2)环化反应以化学选择性和平滑的方式生成了广泛的单酯官能化硅环己烯。研究发现，只有我们新开发的含P-中心和两个羟基的Ar-Binmol-Phos在Rh和铜助催化剂的协同作用下表现出了良好的化学选择性，其中Rh/Cu共催化硅环丁烷与芳丙酸型内炔的(4+2)环化反应导致了结构多样的1-Sila-2-环己烯的合成，产率中等到很好。以芳环上含有3，5-叔丁基取代基的手性Ar-BINMOL-Phos作为手性P-配体，在Rh和Cu的协同催化下，在硅中心手性点手性获得了良好的对映体选择性。
Silicon/carbon switching strategy, known as silasubstitution, plays an important role in drug discovery and material science. However, there is a dearth of efficient and precisely controlled methods for the introduction of a silicon center on complex molecules, which limits advances in the development of silicon-containing drug-like molecules. Here, we disclose an unprecendented process for the synthesis of six-membered functional silacycles based on multifunctional phosphine-promoted bimetallic Rh/Cu-catalyzed Si–C bond activation. The corresponding (4 + 2) annulation reaction chemoselectively and smoothly generates a wide range of monoester-functional silacyclohexenes. And it was found that only our newly developed Ar-BINMOL-Phos bearing a P-center and two hydroxyl groups exhibited perfect chemoselectivity with the aid of the cooperation of rhodium and copper co-catalysts, in which the Rh/Cu co-catalyzed (4 + 2) annulation of silacyclobutanes with arylpropiolate-type internal alkynes led to a facile synthesis of structurally diverse 1-sila-2-cyclohexenes with moderate to good yields. And with a chiral Ar-BINMOL-Phos bearing 3,5-tert-butyl substitutions on the aryl ring as a chiral P-ligand, good enantioselectivity at the “silicon-center” point chirality of the desired silicon-stereogenic silacycles was achieved under the cooperative catalysis of rhodium and copper.