Combined Experimental and Computational Mechanistic Investigation of the Palladium-Catalyzed Decarboxylative Cross-Coupling of Sodium Benzoates with Chloroarenes

被引：4

作者：

Humke, Jenna N. ^{[1
]}

Daley, Ryan A. ^{[1
]}

Morrenzin, Aaron S. ^{[2
]}

Neufeldt, Sharon R. ^{[2
]}

Topczewski, Joseph J. ^{[1
]}

机构：

[1] Univ Minnesota Twin Cities, Dept Chem, Minneapolis, MN 55455 USA

[2] Montana State Univ, Dept Chem & Biochem, Bozeman, MT 59717 USA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2021年 / 86卷 / 17期

基金：

美国国家科学基金会;

关键词：

HETEROAROMATIC CARBOXYLIC-ACIDS; DENSITY-FUNCTIONAL THEORY; OXIDATIVE ADDITION; IN-SITU; C-C; ELECTRONIC-PROPERTIES; SILVER BENZOATE; ARYL BROMIDES; HECK REACTION; COMPLEXES;

D O I：

10.1021/acs.joc.1c00910

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Reported herein is a mechanistic investigation into the palladium-catalyzed decarboxylative cross-coupling of sodium benzoates and chloroarenes. The reaction was found to be first-order in Pd. A minimal substituent effect was observed with respect to chloroarene, and the reaction was zero-order with respect to chloroarene. Palladium-mediated decarboxylation was assigned as the turnover-limiting step based on an Eyring plot and density functional theory computations. Catalyst performance was found to vary based on the electrophile, which is best explained by catalyst decomposition at Pd(0). The 1,5-cyclooctadiene (COD) ligand contained in the precatalyst CODPd(CH2TMS)(2) (Pd1) was shown to be a beneficial additive. The bench-stable Buchwald complex XPhosPdG2 could be used with exogenous COD and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) instead of complex Pd1. Adding exogenous XPhos significantly increased the catalyst turnover number and enhanced reproducibility.

引用

页码：11419 / 11433

页数：15

共 95 条

[1] Predicting reaction performance in C-N cross-coupling using machine learning
Ahneman, Derek T.
Estrada, Jesus G.
Lin, Shishi
Dreher, Spencer D.
Doyle, Abigail G.
[J]. SCIENCE, 2018, 360 (6385) : 186 - 190
[2] EVIDENCE FOR THE LIGATION OF PALLADIUM(0) COMPLEXES BY ACETATE IONS - CONSEQUENCES ON THE MECHANISM OF THEIR OXIDATIVE ADDITION WITH PHENYL IODIDE AND PHPD(OAC)(PPH(3))(2) AS INTERMEDIATE IN THE HECK REACTION
AMATORE, C
CARRE, E
JUTAND, A
MBARKI, MA
MEYER, G
[J]. ORGANOMETALLICS, 1995, 14 (12) : 5605 - 5614
[3] MECHANISM OF OXIDATIVE ADDITION OF PALLADIUM(0) WITH AROMATIC IODIDES IN TOLUENE, MONITORED AT ULTRAMICROELECTRODES
AMATORE, C
PFLUGER, F
[J]. ORGANOMETALLICS, 1990, 9 (08) : 2276 - 2282
[4] EVIDENCE OF THE FORMATION OF ZEROVALENT PALLADIUM FROM PD(OAC)2 AND TRIPHENYLPHOSPHINE
AMATORE, C
JUTAND, A
MBARKI, MA
[J]. ORGANOMETALLICS, 1992, 11 (09) : 3009 - 3013
[5] Formation of palladium(0) complexes from Pd(OAc)2 and a bidentate phosphine ligand (dppp) and their reactivity in oxidative addition
Amatore, C
Jutand, A
Thuilliez, A
[J]. ORGANOMETALLICS, 2001, 20 (15) : 3241 - 3249
[6] Role of dba in the reactivity of palladium(0) complexes generated in situ from mixtures of Pd(dba)2 and phosphines
Amatore, C
Jutand, A
[J]. COORDINATION CHEMISTRY REVIEWS, 1998, 178 : 511 - 528
[7] 3,4-Propylenedioxypyrrole-Based Conjugated Oligomers via Pd-Mediated Decarboxylative Cross Coupling
Arroyave, Frank A.
Reynolds, John R.
[J]. ORGANIC LETTERS, 2010, 12 (06) : 1328 - 1331
[8] Structural insights into active catalyst structures and oxidative addition to (biaryl)phosphine - Palladium complexes via density functional theory and experimental studies
Barder, Timothy E.
Biscoe, Mark R.
Buchwald, Stephen L.
[J]. ORGANOMETALLICS, 2007, 26 (09) : 2183 - 2192
[9] Copper and silver benzoate and aryl complexes and their implications for oxidative decarboxylative coupling reactions
Baur, Andreas
Bustin, Katelyn A.
Aguilera, Ellen
Petersen, Jeffrey L.
Hoover, Jessica M.
[J]. ORGANIC CHEMISTRY FRONTIERS, 2017, 4 (04): : 519 - 524
[10] The Complementary Competitors: Palladium and Copper in C-N Cross-Coupling Reactions
Beletskaya, Irina P.
Cheprakov, Andrei V.
[J]. ORGANOMETALLICS, 2012, 31 (22) : 7753 - 7808

← 1 2 3 4 5 6 7 8 9 10 →