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

页码：2082 / 2090

页数：9

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