Regioselective methylation of methyl glycopyranosides with diazomethane in the presence of transition-metal chlorides and of boric acid

被引：16

作者：

Evtushenko, EV ^{[1
]}

机构：

[1] Russian Acad Sci, Far E Branch, Pacific Inst Bioorgan Chem, Vladivostok 690022, Russia

来源：

CARBOHYDRATE RESEARCH | 1999年 / 316卷 / 1-4期

关键词：

methyl ethers; methyl glycopyranosides; partial methylation; diazomethane; transition metals;

D O I：

10.1016/S0008-6215(99)00044-0

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

Partial methylation of the methyl pyranosides of a number of pentoses, hexoses, 6-deoxyhexoses, methyl uronates and their methyl ethers with diazomethane in the presence of transition-metal chlorides and boric acid was studied. It was found for methyl glycosides of pentoses and 6-deoxyhexoses that tin(II), antimony(III), and titanium(IV) chlorides as well as boric acid promoted substitution mainly of OH-3, but with cerium(III) and zinc(II) salts mainly substitution of OH-2 was observed. Methylation of methyl beta-L-rhamnopyranoside demonstrated higher reactivity of OH-2 in all cases. The methylation of methyl glycosides of hexoses in the presence of tin(II), antimony(III) and cerium(III) chlorides gave mainly 3-methyl ethers. The 3-methyl ethers, which are not involved in further complexation, accumulated up to 50-80% of the reaction mixture (95-100% of monomethyl ether fraction). Convenient preparative syntheses of methyl ethers for a number of sugars are suggested. (C) 1999 Elsevier Science Ltd. All rights reserved.

引用

页码：187 / 200

页数：14

共 41 条

[21] Concerning new dicarbonyl sugars. [J].

Helferich, B ;

Himmen, E .

BERICHTE DER DEUTSCHEN CHEMISCHEN GESELLSCHAFT, 1929, 62 :2136-2141

[22] The specificity of alpha-glucosidase from yeast. [J].

Helferich, B ;

Klein, W ;

Scafer, W .

BERICHTE DER DEUTSCHEN CHEMISCHEN GESELLSCHAFT, 1926, 59 :79-85

[23]

HONIG H, 1975, SYNTHESIS-STUTTGART, P804

[24] Relations between rotatory power and structure in the sugar group. VI. The rotatory powers of the alpha and beta forms of methyl d-xyloside and of methyl l-arabinoside [J].

Hudson, CS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1925, 47 :265-268

[25] METHYL 3-O-METHYL-ALPHA-D-GLUCOPYRANOSIDE AND DERIVATIVES [J].

JEANLOZ, RW ;

GUT, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1954, 76 (22) :5793-5794

[26]

KOVAC P, 1973, CARBOHYD RES, V31, P323, DOI 10.1016/S0008-6215(00)86196-0

[27] A SINGLE-STEP SYNTHESIS OF METHYL 3-O-METHYL-ALPHA-D-MANNO-PYRANOSIDE, 3-O-METHYL-ALPHA-D-GALACTO-PYRANOSIDE, 3-O-METHYL-ALPHA-L-RHAMNO-PYRANOSIDE, AND 3-O-METHYL-ALPHA-L-FUCO-PYRANOSIDE [J].

LIAO, WS ;

LIU, Y ;

LU, DP .

CARBOHYDRATE RESEARCH, 1994, 260 (01) :151-154

[28]

NASHED MA, 1978, CARBOHYD RES, V60, P200

[29] Preparation of methyl glucosides of methylated glucoses [J].

Oldham, JWH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1934, 56 :1360-1362

[30] Relations between rotatory power and structure in the sugar group XII The preparation and properties of pure alpha-methyl d-lyxoside [J].

Phelps, FP ;

Hudson, CS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1926, 48 (01) :503-507

← 1 2 3 4 5 →