A syn outer-sphere oxidative addition: the reaction mechanism in Pd/Senphos-catalyzed carboboration of 1,3-enynes

被引：13
|
作者：
Wang, Ziyong [1 ]
Lamine, Walid [2 ]
Miqueu, Karinne [2 ]
Liu, Shih-Yuan [1 ,2 ]
机构：
[1] Boston Coll, Dept Chem, Chestnut Hill, MA 02467 USA
[2] Univ Pau & Pays Adour, E2S UPPA CNRS, Inst Sci Analyt & Physicochim Environm & Mat IPREM, Helioparc,2 Ave P Angot, F-64053 Pau 09, France
来源：
CHEMICAL SCIENCE | 2023年 / 14卷 / 08期
基金：
美国国家卫生研究院;
关键词：
ALKENYL BORONIC ACIDS; STEREOSELECTIVE-SYNTHESIS; EFFICIENT METHOD; RECENT PROGRESS; ALKYNES; TAMOXIFEN; ALKYNYLBORATION; OLEFINS; BOND; ARYL;
D O I：
10.1039/d2sc05828f
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report a combined experimental and computational study of Pd/Senphos-catalyzed carboboration of 1,3-enynes utilizing DFT calculations, P-31 NMR study, kinetic study, Hammett analysis and Arrhenius/Eyring analysis. Our mechanistic study provides evidence against the conventional inner-sphere beta-migratory insertion mechanism. Instead, a syn outer-sphere oxidative addition mechanism featuring a Pd-pi-allyl intermediate followed by coordination-assisted rearrangements is consistent with all the experimental observations.
引用
收藏
页码：2082 / 2090
页数：9
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