A non-diazo strategy to cyclopropanation via oxidatively generated gold carbene: The benefit of a conformationally rigid P,N-bidentate ligand

被引：56

作者：

Ji, Kegong ^{[1
]}

Zhang, Liming ^{[1
]}

机构：

[1] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA

来源：

ORGANIC CHEMISTRY FRONTIERS | 2014年 / 1卷 / 01期

关键词：

CYCLIZATION;

D O I：

10.1039/c3qo00080j

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

What a trade: diazo ketones for alkynes? By utilizing a conformationally rigid P,N-bidentate ligand, highly efficient intramolecular cyclopropanation reactions using flexible and electronically neutral terminal alkyne substrates are realized via a sterically shielded tri-coordinated gold carbene intermediate. Bicyclic/tricyclic functionalized cyclopropyl ketones are formed in mostly good yields in three steps from readily available enones/enals, which compares favorably with related strategies based on the diazo approach in terms of step economy and operational safety. With this chemistry, we have expanded alkynes as surrogates of alpha-diazo ketones to cyclopropanation reactions.

引用

页码：34 / 38

页数：5

共 27 条

[1] Gold-Catalyzed Oxidative Cyclizations of cis-3-En-1-ynes To Form Cyclopentenone Derivatives [J].

Bhunia, Sabyasachi ;

Ghorpade, Satish ;

Huple, Deepak B. ;

Liu, Rai-Shung .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (12) :2939-2942

[2] Gold-catalyzed synthesis of substituted 2-aminofurans via formal [4+1]-cycloadditions on 3-en-1-ynamides [J].

Dateer, Ramesh B. ;

Pati, Kamalkishore ;

Liu, Rai-Shung .

CHEMICAL COMMUNICATIONS, 2012, 48 (57) :7200-7202

[3] Site-specific introduction of gold-carbenoids by intermolecular oxidation of ynamides or ynol ethers [J].

Davies, Paul W. ;

Cremonesi, Alex ;

Martin, Nicolas .

CHEMICAL COMMUNICATIONS, 2011, 47 (01) :379-381

[4]

Doyle M. P., 1998, MODERN CATALYTIC MET

[5] An Efficient [2+2+1] Synthesis of 2,5-Disubstituted Oxazoles via Gold-Catalyzed Intermolecular Alkyne Oxidation [J].

He, Weimin ;

Li, Chaoqun ;

Zhang, Liming .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (22) :8482-8485

[6] Biarylphosphonite Gold(I) Complexes as Superior Catalysts for Oxidative Cyclization of Propynyl Arenes into Indan-2-ones [J].

Henrion, Guilhem ;

Chavas, Thomas E. J. ;

Le Goff, Xavier ;

Gagosz, Fabien .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (24) :6277-6282

[7] Optimizing P,N-Bidentate Ligands for Oxidative Gold Catalysis: Efficient Intermolecular Trapping of α-Oxo Gold Carbenes by Carboxylic Acids [J].

Ji, Kegong ;

Zhao, Yulong ;

Zhang, Liming .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (25) :6508-6512

[8] Gold-catalyzed cycloisomerizations of enynes:: A mechanistic perspective [J].

Jimenez-Nunez, Eloisa ;

Echavarren, Antonio M. .

CHEMICAL REVIEWS, 2008, 108 (08) :3326-3350

[9] Nature of the Intermediates in Gold(I)-Catalyzed Cyclizations of 1,5-Enynes [J].

Lopez-Carrillo, Veronica ;

Huguet, Nuria ;

Mosquera, Angeles ;

Echavarren, Antonio M. .

CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (39) :10972-10978

[10] Gold-Catalyzed Highly Regioselective Oxidation of C-C Triple Bonds without Acid Additives: Propargyl Moieties as Masked α,β-Unsaturated Carbonyls [J].

Lu, Biao ;

Li, Chaoqun ;

Zhang, Liming .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (40) :14070-14072

← 1 2 3 →