Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C-H Coupling Reaction
Theoretical Elucidation of Potential Enantioselectivity in a Pd-Catalyzed Aromatic C-H Coupling Reaction
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DOI：
10.1021/acs.joc.6b02675
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发表时间：
2017-05-05
影响因子：
3.6
通讯作者：
Irle, Stephan
中科院分区：
文献类型：
--
作者：
Nishimoto, Yoshio;Kondo, Hiroki;Irle, Stephan
对 Pd 催化剂下杂芳烃与芳基硼酸之间的芳香族 C-H 偶联反应机理进行了理论和实验研究。我们将 C-B 金属转移确定为速率决定步骤。发现 (S)-催化剂-反应物复合物通过甲苯基上的 pi 轨道与催化剂配体中的 S-O sigma* 反键轨道之间的超共轭来稳定。我们的研究结果为设计具有更高立体选择性的新型改进钯催化剂提供了思路。
The mechanism of an aromatic C-H coupling reaction between heteroarenes and arylboronic acids using a Pd catalyst was theoretically and experimentally investigated. We identified the C-B transmetalation as the rate determining step. The (S)-catalyst-reactant complex was found to be stabilized by hyperconjugation between pi-orbitals on the tolyl group and the S-O sigma* antibonding orbital in the catalyst ligand. Our findings suggest routes for the design of new, improved Pd catalysts with higher stereoselectivity.