Selective Catalytic Oxidation of Unprotected Carbohydrates

被引:57
作者
Chung, Kevin [1 ]
Waymouth, Robert M. [1 ]
机构
[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA
关键词
selective oxidation; homogeneous catalysis; carbohydrates; palladium; solvent effects; aerobic; alcohol oxidation; REGIOSELECTIVE OXIDATION; ANTITUMOR ANTIBIOTICS; GLYCOSYL AZIDES; POLYOLS; DESIGN;
D O I
10.1021/acscatal.6b01501
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
The development of new strategies for the direct catalytic functionalization of unprotected carbohydrates would be an enabling advance for glycoscience. Herein we report that the catalytic oxidation of unprotected carbohydrates can be carried out selectively with [(neocuproine)Pd(OAc)](2)(OTf)(2) (1) to generate the 3-ketoses. Catalytic aerobic oxidation can be carried out with Pd loadings as low as 1% in the presence of phenolic additives. Catalytic oxidation of a variety of unprotected pyranosides in acetonitrile or acetonitrile/water with Pd catalyst 1 with either oxygen or benzoquinone selectively generates the 3-ketoses. Minor amounts of the 4-ketoses are formed competitively, particularly in the case of pyranosides bearing axial substituents at C4 of the pyranoside. Catalytic oxidations can also be carried out in trifluorethanol, but for pyranosides bearing axial substituents at C2 or C4, selective oxidation to the 3-ketose is accompanied by epimerization to afford the equatorial 3-ketoses. Catalytic oxidation of unprotected hexafuranosides or sialic acid derivatives occurs selectively at the exocyclic diol or triol in trifluoroethanol to generate exocyclic hydroxyketones.
引用
收藏
页码:4653 / 4659
页数:7
相关论文
共 49 条
[1]   Deuteration enhances catalyst lifetime in palladium-catalysed alcohol oxidation [J].
Armenise, Nicola ;
Tahiri, Nabil ;
Eisink, Niek N. H. M. ;
Denis, Mathieu ;
Jager, Manuel ;
De Vries, Johannes G. ;
Witte, Martin D. ;
Minnaard, Adriaan J. .
CHEMICAL COMMUNICATIONS, 2016, 52 (10) :2189-2191
[2]   Organocatalytic Ring-Opening Polymerization of Morpholinones: New Strategies to Functionalized Polyesters [J].
Blake, Timothy R. ;
Waymouth, Robert M. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (26) :9252-9255
[3]   TEMPO-mediated oxidation of polysaccharides: survey of methods and applications [J].
Bragd, PL ;
van Bekkum, H ;
Besemer, AC .
TOPICS IN CATALYSIS, 2004, 27 (1-4) :49-66
[4]   Selective oxidation of unprotected carbohydrates to aldehyde analogues by using TEMPO salts [J].
Breton, Tony ;
Bashiardes, George ;
Leger, Jean-Michel ;
Kokoh, Kouakou B. .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2007, 2007 (10) :1567-1570
[5]   Regioselective One-Pot Protection of D-Glucosamine [J].
Chang, Ken-Lien ;
Zulueta, Medel Manuel L. ;
Lu, Xin-An ;
Zhong, Yong-Qing ;
Hung, Shang-Cheng .
JOURNAL OF ORGANIC CHEMISTRY, 2010, 75 (21) :7424-7427
[6]   Chemoselective Pd-Catalyzed Oxidation of Polyols: Synthetic Scope and Mechanistic Studies [J].
Chung, Kevin ;
Banik, Steven M. ;
De Crisci, Antonio G. ;
Pearson, David M. ;
Blake, Timothy R. ;
Olsson, Johan V. ;
Ingram, Andrew J. ;
Zare, Richard N. ;
Waymouth, Robert M. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (20) :7593-7602
[7]   Regioselectively trisilylated hexopyranosides through homogeneously catalyzed silane alcoholysis [J].
Chung, MK ;
Schlaf, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (51) :18085-18092
[8]   Aerobic alcohol oxidation with cationic palladium complexes: insights into catalyst design and decomposition [J].
Conley, Nicholas R. ;
Labios, Liezel A. ;
Pearson, David M. ;
McCrory, Charles C. L. ;
Waymouth, Robert M. .
ORGANOMETALLICS, 2007, 26 (23) :5447-5453
[9]  
David S., 1997, Preparative Carbohydrate Chemistry, P69
[10]   Chemoselective Oxidation of Polyols with Chiral Palladium Catalysts [J].
De Crisci, Antonio G. ;
Chung, Kevin ;
Oliver, Allen G. ;
Solis-Ibarra, Diego ;
Waymouth, Robert M. .
ORGANOMETALLICS, 2013, 32 (07) :2257-2266