Exploring Cooperative Effects in Oxidative NHC Catalysis: Regioselective Acylation of Carbohydrates

被引：37

作者：

Cramer, David L. ^{[1
]}

Bera, Srikrishna ^{[1
]}

Studer, Armido ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, Corrensstr 40, D-48149 Munster, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 22期

关键词：

carbohydrates; cooperative catalysis; Nheterocyclic carbene; organocatalysis; synthetic methods; N-HETEROCYCLIC CARBENES; KINETIC RESOLUTION; CHEMOSELECTIVE ACYLATION; TRIAZOLIUM SALTS; SILYL PROTECTION; AMINO-ALCOHOLS; FUNCTIONALIZATION; RECOGNITION; 1,2-DIOLS; ESTERS;

D O I：

10.1002/chem.201601398

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The utility of oxidative NHC catalysis for both the regioselective and chemoselective functionalization of carbohydrates is explored. Chiral NHCs allow for the highly regioselective oxidative esterification of various carbohydrates using aldehydes as acylation precursors. The transformation was also shown to be amenable to both cis/trans diol isomers, free amino groups, and selective for specific sugar epimers in competition experiments. Efficiency and regioselectivity of the acylation can be improved upon using two different NHC catalysts that act cooperatively. The potential of the method is documented by the regioselective acylation of an amino-linked neodisaccharide.

引用

页码：7403 / 7407

页数：5

共 51 条

[1] Investigations into the synthesis of amine-linked neodisaccharides [J].

Akhtar, Tashfeen ;

Cumpstey, Ian .

TETRAHEDRON LETTERS, 2007, 48 (49) :8673-8677

[2] Chiral Copper(II) Complex-Catalyzed Reactions of Partially Protected Carbohydrates [J].

Allen, C. Liana ;

Miller, Scott J. .

ORGANIC LETTERS, 2013, 15 (24) :6178-6181

[3] Concerted Amidation of Activated Esters: Reaction Path and Origins of Selectivity in the Kinetic Resolution of Cyclic Amines via N-Heterocyclic Carbenes and Hydroxamic Acid Cocatalyzed Acyl Transfer [J].

Allen, Scott E. ;

Hsieh, Sheng-Ying ;

Gutierrez, Osvaldo ;

Bode, Jeffrey W. ;

Kozlowski, Marisa C. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (33) :11783-11791

[4] Exploring the use of conformationally locked aminoglycosides as a new strategy to overcome bacterial resistance [J].

Bastida, A ;

Hidalgo, A ;

Chiara, JL ;

Torrado, M ;

Corzana, F ;

Pérez-Cañadillas, JM ;

Groves, P ;

Garcia-Junceda, E ;

Gonzalez, C ;

Jimenez-Barbero, J ;

Asensio, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (01) :100-116

[5] Site-Selective Displacement of Tobramycin Hydroxyls for Preparation of Antimicrobial Cationic Amphiphiles [J].

Berkov-Zrihen, Yifat ;

Herzog, Ido M. ;

Feldman, Mark ;

Fridman, Micha .

ORGANIC LETTERS, 2013, 15 (24) :6144-6147

[6] Practical Silyl Protection of Ribonucleosides [J].

Blaisdell, Thomas P. ;

Lee, Sunggi ;

Kasaplar, Pinar ;

Sun, Xixi ;

Tan, Kian L. .

ORGANIC LETTERS, 2013, 15 (18) :4710-4713

[7] Investigation of benzoyloximes as benzoylating reagents: benzoyl-Oxyma as a selective benzoylating reagent [J].

Burugupalli, Satvika ;

Shah, Sayali ;

van der Peet, Phillip L. ;

Arora, Seep ;

White, Jonathan M. ;

Williams, Spencer J. .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2016, 14 (01) :97-104

[8] Recognition and Site-Selective Transformation of Monosaccharides by Using Copper(II) Catalysis [J].

Chen, I-Hon ;

Kou, Kevin G. M. ;

Le, Diane N. ;

Rathbun, Colin M. ;

Dong, Vy M. .

CHEMISTRY-A EUROPEAN JOURNAL, 2014, 20 (17) :5013-5018

[9]

Collett Christopher J, 2015, Angew Chem Weinheim Bergstr Ger, V127, P6991

[10] Rate and Equilibrium Constants for the Addition of N-Heterocyclic Carbenes into Benzaldehydes: A Remarkable 2-Substituent Effect [J].

Collett, Christopher J. ;

Massey, Richard S. ;

Taylor, James E. ;

Maguire, Oliver R. ;

O'Donoghue, AnnMarie C. ;

Smith, Andrew D. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (23) :6887-6892

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