Cobalt-Catalyzed Benzylic Borylation: Enabling Polyborylation and Functionalization of Remote, Unactivated C(sp3)-H Bonds

被引：180

作者：

Palmer, W. Neil ^{[1
]}

Obligacion, Jennifer V. ^{[1
]}

Pappas, Iraklis ^{[1
]}

Chirik, Paul J. ^{[1
]}

机构：

[1] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2016年 / 138卷 / 03期

基金：

美国国家科学基金会;

关键词：

C-H BORYLATION; DIASTEREOSELECTIVE SYNTHESIS; METHYL-GROUP; ARENES; CONSTRUCTION; ACTIVATION; HETEROARENES; COMPLEXES; NICKEL; IRON;

D O I：

10.1021/jacs.5b12249

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Cobalt dialkyl and bis(carboxylate) complexes bearing a-diimine ligands have been synthesized and demonstrated as active for the C(sp(3))-H borylation of a range of substituted alkyl arenes using B(2)Pin(2) (Pin = pinacolate) as the boron source. At longer reaction times, rare examples of polyborylation were observed, and in the case of toluene, all three benzylic C-H positions were functionalized. Coupling benzylic C-H activation with alkyl isomerization enabled a base-metal-catalyzed method for the borylation of remote, unactivated C(sp(3))-H bonds.

引用

收藏

页码：766 / 769

页数：4

相关论文

共 68 条

[31] Iridium-catalyzed borylation of arenes and heteroarenes via C-H activation [J].

Ishiyama, Tatsuo ;

Miyaura, Norio .

PURE AND APPLIED CHEMISTRY, 2006, 78 (07) :1369-1375

[32] Silver(I)-Catalyzed Diastereoselective Synthesis of anti-1,2-Hydroxyboronates [J].

Joannou, Matthew V. ;

Moyer, Brandon S. ;

Goldfogel, Matthew J. ;

Meek, Simon J. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (47) :14141-14145

[33] Enantio- and Diastereoselective Synthesis of 1,2-Hydroxyboronates through Cu-Catalyzed Additions of Alkylboronates to Aldehydes [J].

Joannou, Matthew V. ;

Moyer, Brandon S. ;

Meek, Simon J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (19) :6176-6179

[34] COMPARATIVE REACTIVITIES OF HYDROCARBON C-H BONDS WITH A TRANSITION-METAL COMPLEX [J].

JONES, WD ;

FEHER, FJ .

ACCOUNTS OF CHEMICAL RESEARCH, 1989, 22 (03) :91-100

[35] Synthesis of Primary and Secondary Alkylboronates through Site-Selective C(sp3)-H Activation with Silica-Supported Monophosphine-Ir Catalysts [J].

Kawamorita, Soichiro ;

Murakami, Ryo ;

Iwai, Tomohiro ;

Sawamura, Masaya .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (08) :2947-2950

[36] Rh-Catalyzed Borylation of N-Adjacent C(sp3)-H Bonds with a Silica-Supported Triarylphosphine Ligand [J].

Kawamorita, Soichiro ;

Miyazaki, Tatsuya ;

Iwai, Tomohiro ;

Ohmiya, Hirohisa ;

Sawamura, Masaya .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (31) :12924-12927

[37] Rh-Catalyzed Ortho-Selective C-H Borylatiob of N-Functionalized Arenes with Silica-Supported Bridgehead Monophosphine Ligands [J].

Kawamorita, Soichiro ;

Miyazaki, Tatsuya ;

Ohmiya, Hirohisa ;

Iwai, Tomohiro ;

Sawamura, Masaya .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (48) :19310-19313

[38] Iridium-Catalyzed Borylation of Primary Benzylic C-H Bonds without a Directing Group: Scope, Mechanism, and Origins of Selectivity [J].

Larsen, Matthew A. ;

Wilson, Conner V. ;

Hartwig, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (26) :8633-8643

[39] Iridium-Catalyzed C-H Borylation of Heteroarenes: Scope, Regioselectivity, Application to Late-Stage Functionalization, and Mechanism [J].

Larsen, Matthew A. ;

Hartwig, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (11) :4287-4299

[40] Metal-free catalytic C-H bond activation and borylation of heteroarenes [J].

Legare, Marc-Andre ;

Courtemanche, Marc-Andre ;

Rochette, Etienne ;

Fontaine, Frederic-Georges .

SCIENCE, 2015, 349 (6247) :513-516

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