Pd-Catalyzed Organometallic-Free Homologation of Arylboronic Acids Enabled by Chemoselective Transmetalation

被引：7

作者：

Bastick, Kane A. C. ^{[1
]}

Watson, Allan J. B. ^{[1
]}

机构：

[1] Univ St Andrews, Sch Chem, EaStCHEM, St Andrews KY16 9ST, Fife, Scotland

来源：

ACS CATALYSIS | 2023年 / 13卷 / 10期

基金：

英国工程与自然科学研究理事会;

关键词：

boron; catalysis; chemoselectivity; cross-coupling; homologation; palladium; BORONIC ESTERS; HECK REACTION; BORYLATION; ARYL; PROTODEBORONATION; HALIDES; VINYL;

D O I：

10.1021/acscatal.3c00921

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A Pd-catalyzed homologation of arylboronic acids is reported. Halomethylboronic acid pinacol esters (Bpin) undergo a remarkably facile, yet rare, oxidative addition enabled by an alpha-boryl effect. Simultaneous chemoselective transmetalation allows use of these metalloid reagents for formal C1 insertion to deliver benzyl Bpin products without the requirement for stoichiometric organometallic reagents. The utility of the process is demonstrated by stepwise C(sp3)-C(sp2) cross-coupling of the boronic ester products into diarylmethane pharmacophores and electrophile/ nucleophile chemoselective cross-coupling. Control experiments that demonstrate the reactivity enhancement provided by the alpha- boryl effect are provided, along with a description of the limitations of the formal homologation process.

引用

页码：7013 / 7018

页数：6

共 50 条

[41] Synthesis of allenamides by Pd-catalyzed coupling of 3-alkoxycarbonyloxy ynamides or 1-alkoxycarbonyloxy allenamides with arylboronic acids
Cao, Jian
Kong, Yulong
Deng, Yuan
Lai, Guoqiao
Cui, Yuming
Hu, Ziqiang
Wang, Guanhai
ORGANIC & BIOMOLECULAR CHEMISTRY, 2012, 10 (48) : 9556 - 9561
[42] Synthesis of β,β-Disubstituted lndanones via the Pd-Catalyzed Tandem Conjugate Addition/Cyclization Reaction of Arylboronic Acids with α,β-Unsaturated Esters
Gao, Ang
Liu, Xiu-Yan
Li, Hao
Ding, Chang-Hua
Hou, Xue-Long
JOURNAL OF ORGANIC CHEMISTRY, 2017, 82 (19): : 9988 - 9994
[43] Pd-Catalyzed Oxidative Aminocarbonylation of Arylboronic Acids with Unreactive Tertiary Amines via C-N Bond Activation
Kolekar, Yuvraj A.
Bhanage, Bhalchandra M.
JOURNAL OF ORGANIC CHEMISTRY, 2021, 86 (20): : 14028 - 14035
[44] Pd-catalyzed Suzuki-Miyaura cross-coupling of [Ph2SR][OTf] with arylboronic acids
Wang, Xiao-Yan
Song, Hai-Xia
Wang, Shi-Meng
Yang, Jing
Qin, Hua-Li
Jiang, Xin
Zhang, Cheng-Pan
TETRAHEDRON, 2016, 72 (47) : 7606 - 7612
[45] Pd-catalyzed divergent trifluoroethylation and arylation of arylboronic acids by aryl( 2,2,2-trifluoroethyl)iodonium triflates
Yang, Jing
Han, Qiu-Yan
Zhao, Cheng-Long
Dong, Tao
Hou, Zhi-Yuan
Qin, Hua-Li
Zhang, Cheng-Pan
ORGANIC & BIOMOLECULAR CHEMISTRY, 2016, 14 (32) : 7654 - 7658
[46] Synthesis of 2-Arylpiperidines via Pd-Catalyzed Arylation of Aza-Achmatowicz Rearrangement Products with Arylboronic Acids
Zhao, Guodong
Canterbury, Daniel P.
Taylor, Alexandria P.
Cheng, Xiayun
Mikochik, Peter
Bagley, Scott W.
Tong, Rongbiao
ORGANIC LETTERS, 2020, 22 (02) : 458 - 463
[47] Pd-catalyzed asymmetric conjugate addition of arylboronic acids to 2-nitroacrylates: a facile route to β2-homophenylglycines
Petri, Andreas
Seidelmann, Oliver
Eilitz, Uwe
Lessmann, Frank
Reissmann, Stefan
Wendisch, Volkmar
Gutnov, Andrey
TETRAHEDRON LETTERS, 2014, 55 (01) : 267 - 270
[48] Vinylidenation of Organoboronic Esters Enabled by a Pd-Catalyzed Metallate Shift
Aparece, Mark D.
Gao, Chenpeng
Lovinger, Gabriel J.
Morken, James P.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2019, 58 (02) : 592 - 595
[49] The Direct Pd-Catalyzed γ-Lactonization of Aliphatic Carboxylic Acids
Xu, Tianxiao
Mal, Sourjya
van Gemmeren, Manuel
ACS CATALYSIS, 2025, 15 (04): : 2735 - 2741
[50] A green protocol for the Pd catalyzed ligand free homocoupling reaction of arylboronic acids under ambient conditions
Dwivedi, Seema
Bardhan, Soumik
Ghosh, Prasanjit
Das, Sajal
RSC ADVANCES, 2014, 4 (77) : 41045 - 41050

← 1 2 3 4 5 →