金属-配体协同促进的金催化末端炔烃的均/异二聚反应
Gold-Catalyzed Homo/Heterodimerization of Terminal Alkynes Facilitated by Metal-Ligand Cooperation.
作者信息
Wu Xuan, Zhang Liming
机构信息
Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93117, United States.
出版信息
Org Lett. 2024 Jul 12;26(27):5736-5740. doi: 10.1021/acs.orglett.4c01872. Epub 2024 Jun 27.
Abstract
Gold-catalyzed dimerization of terminal alkynes is achieved under mild reaction conditions and in excellent yields. In addition to homodimerizations, heterodimerizations between TBS acetylene and a range of terminal alkynes were realized using the syringe pump technique. The reaction tolerates various functional groups. The rate acceleration experienced in the reactions is enabled by metal-ligand cooperation. A binaphthyl-2-ylphosphine ligand featuring a 3'-diisopropylphosphoryl group plays a pivotal role in facilitating alkyne attack by accommodating and/or deprotonating its terminal proton.
摘要
在温和的反应条件下，金催化末端炔烃的二聚反应能够以优异的产率实现。除了均二聚反应外，使用注射泵技术实现了叔丁基二甲基硅乙炔与一系列末端炔烃之间的异二聚反应。该反应能耐受各种官能团。反应中经历的速率加速是由金属-配体协同作用实现的。一种带有3'-二异丙基磷酰基的联萘-2-基膦配体在促进炔烃进攻方面起着关键作用，它通过容纳和/或去质子化其末端质子来实现这一点。
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