Gold-Catalyzed Silyl-Migrative Cyclization of Homopropargylic Alcohols Enabled by Bifunctional Biphenyl-2-ylphosphine and DFT Studies
Gold-Catalyzed Silyl-Migrative Cyclization of Homopropargylic Alcohols Enabled by Bifunctional Biphenyl-2-ylphosphine and DFT Studies
复制标题
双官能联苯-2-基膦和 DFT 研究实现金催化均炔醇的甲硅烷基迁移环化
DOI：
10.1021/acs.orglett.9b02735
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发表时间：
2019-10-04
期刊：
影响因子：
5.2
通讯作者：
Zhang, Liming
中科院分区：
文献类型：
--
作者：
Li, Ting;Yang, Yuhan;Zhang, Liming
专为均相金催化定制的新型配体的开发使新的金催化的开发成为可能。在这项工作中，我们报道了一个远程功能化的联苯基-2-基膦配体使金催化的高丙叉醇的环化反应伴随着不寻常的硅基迁移，这为3-硅基-4，5-二氢呋喃提供了有效的途径。密度泛函理论对这一新的转变机理的研究表明，配体的空间主体与其适当位置的远端叔氨基之间存在协同作用，促进了硅基的协同迁移和环状C-O键的形成。
The development of novel ligands specifically tailored for homogeneous gold catalysis permits the development of new gold catalysis. In this work, we report that a remotely functionalized biphenyl-2-ylphosphine ligand enables gold-catalyzed cyclization of homopropargylic alcohols accompanied by an unusual silyl migration, which provides efficient access to 3-silyl-4,5-dihydrofurans. DFT studies of the mechanism of this novel transformation suggest the synergy between the steric bulk of the ligand and its properly positioned remote tertiary amino group in facilitating a concerted silyl migration and cyclative C-O bond formation step.