Dehydrative C-H/N-OH Functionalizations in H2O by Ruthenium(II) Catalysis: Subtle Effect of Carboxylate Ligands and Mechanistic Insight

被引：68

作者：

Yang, Fanzhi ^{[1
]}

Ackermann, Lutz ^{[1
]}

机构：

[1] Univ Gottingen, Inst Organ & Biomol Chem, D-37077 Gottingen, Germany

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2014年 / 79卷 / 24期

基金：

欧洲研究理事会;

关键词：

H BOND ACTIVATION; AEROBIC OXIDATIVE CYCLIZATION; ISOQUINOLONE SYNTHESIS; DIRECT ARYLATIONS; DIRECTING GROUPS; ALKYNES; CONSTRUCTION; HETEROCYCLES; ANNULATIONS; OLEFINATION;

D O I：

10.1021/jo501884v

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A ruthenium(II) complex derived from the electron-deficient aromatic carboxylic acid 3-(F3C)C6H4CO2H proved to be a highly efficient catalyst for dehydrative alkyne annulation by NH-free hydroxamic acids in water. The CH/NOH functionalization occurred with excellent positional selectivity as well as ample substrate scope, setting the stage for effective intermolecular alkenylations of hydroxamic acids. Detailed mechanistic studies were suggestive of a kinetically relevant CH metalation by carboxylate assistance along with subsequent migratory alkyne insertion, reductive elimination, and intramolecular oxidative addition.

引用

页码：12070 / 12082

页数：13

共 58 条

[1] Phosphine oxides as preligands in ruthenium-catalyzed arylations via C-H bond functionalization using aryl chlorides [J].

Ackermann, L .

ORGANIC LETTERS, 2005, 7 (14) :3123-3125

[2] Cobalt-Catalyzed C-H Arylations, Benzylations, and Alkylations with Organic Electrophiles and Beyond [J].

Ackermann, Lutz .

JOURNAL OF ORGANIC CHEMISTRY, 2014, 79 (19) :8948-8954

[3] Carboxylate-Assisted Ruthenium-Catalyzed Alkyne Annulations by C-H/Het-H Bond Functionalizations [J].

Ackermann, Lutz .

ACCOUNTS OF CHEMICAL RESEARCH, 2014, 47 (02) :281-295

[4] Cationic Ruthenium(II) Catalysts for Oxidative C-H/N-H Bond Functionalizations of Anilines with Removable Directing Group: Synthesis of Indoles in Water [J].

Ackermann, Lutz ;

Lygin, Alexander V. .

ORGANIC LETTERS, 2012, 14 (03) :764-767

[5] Ruthenium-Catalyzed C-H/N-O Bond Functionalization: Green Isoquinolone Syntheses in Water [J].

Ackermann, Lutz ;

Fenner, Sabine .

ORGANIC LETTERS, 2011, 13 (24) :6548-6551

[6] Ruthenium-catalyzed aerobic oxidative coupling of alkynes with 2-aryl-substituted pyrroles [J].

Ackermann, Lutz ;

Wang, Lianhui ;

Lygin, Alexander V. .

CHEMICAL SCIENCE, 2012, 3 (01) :177-180

[7] Ruthenium-Catalyzed Oxidative Annulation by Cleavage of C-H/N-H Bonds [J].

Ackermann, Lutz ;

Lygin, Alexander V. ;

Hofmann, Nora .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (28) :6379-6382

[8] Carboxylate-Assisted Transition-Metal-Catalyzed C-H Bond Functionalizations: Mechanism and Scope [J].

Ackermann, Lutz .

CHEMICAL REVIEWS, 2011, 111 (03) :1315-1345

[9] Mechanistic Insight into Direct Arylations with Ruthenium(II) Carboxylate Catalysts [J].

Ackermann, Lutz ;

Vicente, Ruben ;

Potukuchi, Harish K. ;

Pirovano, Valentina .

ORGANIC LETTERS, 2010, 12 (21) :5032-5035

[10] Ruthenium-Catalyzed Direct Arylations Through C-H Bond Cleavages [J].

Ackermann, Lutz ;

Vicente, Ruben .

C-H ACTIVATION, 2010, 292 :211-229

← 1 2 3 4 5 6 →