Solvent Effects in the Nucleophilic Substitutions of Tetrahydropyran Acetals Promoted by Trimethylsilyl Trifluoromethanesulfonate: Trichloroethylene as Solvent for Stereoselective C- and O-Glycosylations

被引：31
作者：
Kendale, Joanna C. [1 ]
Valentin, Elizabeth M. [1 ]
Woerpel, K. A. [1 ]
机构：
[1] NYU, Dept Chem, New York, NY 10003 USA
来源：
ORGANIC LETTERS | 2014年 / 16卷 / 14期
基金：
美国国家卫生研究院;
关键词：
OXOCARBENIUM IONS; STEREOCHEMICAL CONTROL; IONIZING POWER; DONORS; CONSTRUCTION; SCALE; DIASTEREOSELECTIVITY; THIOGLYCOSIDES; INTERMEDIATE; GLYCOSIDES;
D O I：
10.1021/ol501471c
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The selectivities of nucleophilic substitution reactions of tetrahydropyran acetals promoted by trimethylsilyl trifluoromethanesulfonate depend upon the reaction solvent. Polar solvents favor the formation of S(N)1 products, while nonpolar solvents favor S(N)2 products. Trichloroethylene was identified as the solvent most likely to give S(N)2 products in both C- and O-glycosylation reactions.
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收藏
页码：3684 / 3687
页数：4
相关论文
共 58 条
[1]   LINEAR SOLVATION ENERGY RELATIONSHIPS .37. AN ANALYSIS OF CONTRIBUTIONS OF DIPOLARITY POLARIZABILITY, NUCLEOPHILIC ASSISTANCE, ELECTROPHILIC ASSISTANCE, AND CAVITY TERMS TO SOLVENT EFFECTS ON TERT-BUTYL HALIDE SOLVOLYSIS RATES [J].
ABRAHAM, MH ;
DOHERTY, RM ;
KAMLET, MJ ;
HARRIS, JM ;
TAFT, RW .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1987, (07) :913-920
[2]  
Adinolfi M., 2006, EUR J ORG CHEM, V69
[3]   CONVERSION OF N-ACYL-2,3-DIHYDRO-4-PYRIDONES TO 4-CHLORO-1,2-DIHYDROPYRIDINES USING THE VILSMEIER REAGENT - SYNTHESIS OF (-)-CONIINE AND (PLUS-OR-MINUS)-LUPININE [J].
ALAWAR, RS ;
JOSEPH, SP ;
COMINS, DL .
JOURNAL OF ORGANIC CHEMISTRY, 1993, 58 (27) :7732-7739
[4]  
Bard J., 1990, J AM CHEM SOC, V112, P6918
[5]   Erosion of Stereochemical Control with Increasing Nucleophilicity: O-Glycosylation at the Diffusion Limit [J].
Beaver, Matthew G. ;
Woerpel, K. A. .
JOURNAL OF ORGANIC CHEMISTRY, 2010, 75 (04) :1107-1118
[6]   THE SN2-SN1 SPECTRUM .4. THE SN2 (INTERMEDIATE) MECHANISM FOR SOLVOLYSES OF TERT-BUTYL CHLORIDE - A REVISED Y-SCALE OF SOLVENT IONIZING POWER BASED ON SOLVOLYSES OF 1-ADAMANTYL CHLORIDE [J].
BENTLEY, TW ;
CARTER, GE .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1982, 104 (21) :5741-5747
[7]   CONFORMATIONAL-ANALYSIS OF NITRILIUM INTERMEDIATES IN GLYCOSYLATION REACTIONS [J].
BRACCINI, I ;
DEROUET, C ;
ESNAULT, J ;
DUPENHOAT, CH ;
MALLET, JM ;
MICHON, V ;
SINAY, P .
CARBOHYDRATE RESEARCH, 1993, 246 :23-41
[8]   Neighboring-Group Participation by C-2 Ether Functions in Glycosylations Directed by Nitrile Solvents [J].
Chao, Chin-Sheng ;
Lin, Ching-Yu ;
Mulani, Shaheen ;
Hung, Wei-Cheng ;
Mong, Kwok-kong Tony .
CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (43) :12193-12202
[9]   Glycosylation Catalyzed by a Chiral Bronsted Acid [J].
Cox, Daniel J. ;
Smith, Martin D. ;
Fairbanks, Antony J. .
ORGANIC LETTERS, 2010, 12 (07) :1452-1455
[10]   RESPONSE OF TRIFLATES TO SOLVENT IONIZING POWER - A Y OTF SCALE BASED ON 7-NORBORNYL TRIFLATE [J].
CREARY, X ;
MCDONALD, SR .
JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (04) :474-479
123456