协同催化实现内式 1,3-烯炔烃的氢炔丙基化反应。
-Hydroalkynylation of Internal 1,3-Enynes Enabled by Cooperative Catalysis.
机构信息
Department of Chemistry, Boston College, Chestnut Hill, Massachusetts 02467-3860, United States.
Université de Pau et des Pays de l'Adour, E2S UPPA/CNRS, Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux IPREM UMR 5254. Hélioparc, 2 Avenue P. Angot, 64053 Pau Cedex 09, France.
出版信息
J Am Chem Soc. 2023 Mar 15;145(10):5624-5630. doi: 10.1021/jacs.3c00514. Epub 2023 Mar 2.
Abstract
A cooperative catalyst system involving a Pd(0)/Senphos complex, tris(pentafluorophenyl)borane, copper bromide, and an amine base, is demonstrated to catalyze -hydroalkynylation of internal 1,3-enynes. For the first time, a Lewis acid catalyst is shown to promote the reaction involving the emerging outer-sphere oxidative reaction step. The resulting cross-conjugated dieneynes are versatile synthons for organic synthesis, and their characterization reveals distinct photophysical properties depending on the positioning of the donor/acceptor substituents along the conjugation path.
摘要
一种涉及 Pd(0)/Senphos 配合物、三(五氟苯基)硼烷、溴化铜和胺碱的协同催化剂体系，被证明可以催化内部 1,3-烯炔的 -氢炔基化反应。首次表明路易斯酸催化剂可以促进涉及新兴的外球氧化反应步骤的反应。所得的交叉共轭二炔是有机合成的多功能合成子，其特性取决于供体/受体取代基沿共轭路径的定位，表现出不同的光物理性质。
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