Palladium(I)-Iodide-Catalyzed Deoxygenative Heck Reaction of Vinyl Triflates: A Formate-Mediated Cross-Electrophile Reductive Coupling with cine-Substitution

被引：8

作者：

Chang, Yu-Hsiang ^{[1
]}

Shen, Weijia ^{[1
]}

Shezaf, Jonathan Z. ^{[1
]}

Ortiz, Eliezer ^{[1
]}

Krische, Michael J. ^{[1
]}

机构：

[1] Univ Texas Austin, Dept Chem, Austin, TX 78712 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2023年 / 145卷 / 42期

关键词：

DINUCLEAR PD(I) COMPLEXES; CATALYZED ALPHA-ARYLATION; ARYL; BROMIDES; ORGANOSTANNANES; HYDROGENOLYSIS; ACTIVATION; PRODUCTS; DIMER;

D O I：

10.1021/jacs.3c09876

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The first deoxygenative Heck reactions are described, as illustrated by formate-mediated cine-substitutions of vinyl triflates with aryl iodides. The collective data corroborate a mechanism in which Pd(OAc)(2) and Bu4NI form the dianionic iodide-bridged dimer [Pd2I6][NBu4](2), which, under reducing conditions, serves as a precursor to the palladium(I) complex [Pd2I4][NBu4](2). Dinculear oxidative addition of aryl iodide forms [Pd2I5(Ar)][NBu4](2), which dissociates to the monometallic complex [PdI2(Ar)][NBu4]. Vinyl triflate migratory insertion-sulfonate elimination delivers a palladium(IV) carbene, which upon beta-hydride elimination/C-H reductive elimination gives the product of cine-substitution. These processes are the first efficient formate-mediated cross-electrophile reductive couplings beyond carbonyl addition.

引用

页码：22890 / 22895

页数：6

共 3 条

[1] Formate-Mediated Reductive Cross-Coupling of Vinyl Halides and Aryl Iodides: cine-Substitution via Palladium(I) Catalysis
Santana, Catherine G.
Teoh, Yhin Sarah
Evarts, Madeline M.
Shezaf, Jonathan Z.
Krische, Michael J.
ORGANIC LETTERS, 2024, 26 (33) : 7055 - 7059
[2] Formate-Mediated Cross-Electrophile Reductive Coupling of Aryl Iodides and Bromopyridines
Schwartz, Leyah A.
Spielmann, Kim
Swyka, Robert A.
Xiang, Ming
Krische, Michael J.
ISRAEL JOURNAL OF CHEMISTRY, 2021, 61 (5-6) : 298 - 301
[3] Formation of cine-Substitution Products in the SuzukiMiyaura Cross-Coupling Reaction Catalyzed by Dinuclear Palladium Complexes
Tsukada, Naofumi
Abe, Tsubasa
Inoue, Yoshio
HELVETICA CHIMICA ACTA, 2013, 96 (06) : 1093 - 1102

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