methyl 2,6'-O-(1,3-xylylene)-(2,3,4-tri-O-benzyl-β-D-glucopyranosyl)-(1'->3)-4,6-O-benzylidene-α-D-glucopyranoside | 229163-04-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,6'-O-(1,3-xylylene)-(2,3,4-tri-O-benzyl-β-D-glucopyranosyl)-(1'->3)-4,6-O-benzylidene-α-D-glucopyranoside
• 英文别名: (1S,3S,4R,6R,9R,11S,12R,23R,24R,25S,26R)-11-methoxy-6-phenyl-24,25,26-tris(phenylmethoxy)-2,5,7,10,13,21,27-heptaoxapentacyclo[21.3.1.115,19.03,12.04,9]octacosa-15,17,19(28)-triene
• CAS: 229163-04-6
• 化学式: C₄₉H₅₂O₁₁
• 分子量: 816.945
• InChiKey: UGZCOPSWKDTVDY-XFLNUSOMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  60
• 可旋转键数：
  11
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  methyl 2,6'-O-(1,3-xylylene)-(2,3,4-tri-O-benzyl-β-D-glucopyranosyl)-(1'->3)-4,6-O-benzylidene-α-D-glucopyranoside 在 palladium on activated charcoal 甲酸 、 氢气 作用下， 以 甲醇 、 乙酸乙酯 为溶剂， 反应 20.0h， 生成 甲基alpha-D-昆布二糖苷
  参考文献：
  名称：

  Efficient Intramolecular Glycosylation Supported by a Rigid Spacer

  摘要：

  The m-xylylene moiety was employed as rigid spacer in intramolecular glycoside bond formation. Fifteen-membered macrocycle formation starting from 6-O-linked donor and 6- and 4-O-linked acceptor (5a,b, 6b) led exclusively to beta(1-4)- and beta(1-6)-linked compounds 7 beta and 8 beta, respectively, which gave cellobioside and gentiobioside derivatives. The glycosylation yields could be improved by 14-membered macrocycle formation. In the four cases studied, the donor was 6-O-linked to the spacer. For the acceptor linkage to the spacer and the accepting hydroxy group, relative D-/L-threo- and D-/L-erythro-arrangements were chosen. Standard glycosylation conditions led in three cases (13, 14, 23) only to beta-linkage in high yield (16 beta, 17 beta, 25 beta). For the transformation of 24, having a D-erythro-arrangement in the acceptor moiety, the alpha-anomer 26 alpha was preferentially obtained. Limitation of the conformational space of the donor and the acceptor as in 31, which is stereochemically identical with 24, led to the corresponding alpha-glycoside 32 alpha in 87% yield. Synthesis of a pseudo mirror image of 23 [having 6-(D)/3-(D-threo)-arrangement], namely 35, having 3(L)/6-(L-threo)-arrangement of the donor and acceptor moieties, expectedly gave only alpha-glycoside 36 alpha in very high yield. Thus, the efficiency and versatility of this conceptual approach to intramolecular glycoside bond formation is exhibited.

  DOI：

  10.1021/jo990132e
• 作为产物：
  描述：

  ethyl 2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 N-碘代丁二酰亚胺 、 15-冠醚-5 、 三氟甲磺酸 、 sodium hydride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 23.5h， 生成 methyl 2,6'-O-(1,3-xylylene)-(2,3,4-tri-O-benzyl-β-D-glucopyranosyl)-(1'->3)-4,6-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Efficient Intramolecular Glycosylation Supported by a Rigid Spacer

  摘要：

  The m-xylylene moiety was employed as rigid spacer in intramolecular glycoside bond formation. Fifteen-membered macrocycle formation starting from 6-O-linked donor and 6- and 4-O-linked acceptor (5a,b, 6b) led exclusively to beta(1-4)- and beta(1-6)-linked compounds 7 beta and 8 beta, respectively, which gave cellobioside and gentiobioside derivatives. The glycosylation yields could be improved by 14-membered macrocycle formation. In the four cases studied, the donor was 6-O-linked to the spacer. For the acceptor linkage to the spacer and the accepting hydroxy group, relative D-/L-threo- and D-/L-erythro-arrangements were chosen. Standard glycosylation conditions led in three cases (13, 14, 23) only to beta-linkage in high yield (16 beta, 17 beta, 25 beta). For the transformation of 24, having a D-erythro-arrangement in the acceptor moiety, the alpha-anomer 26 alpha was preferentially obtained. Limitation of the conformational space of the donor and the acceptor as in 31, which is stereochemically identical with 24, led to the corresponding alpha-glycoside 32 alpha in 87% yield. Synthesis of a pseudo mirror image of 23 [having 6-(D)/3-(D-threo)-arrangement], namely 35, having 3(L)/6-(L-threo)-arrangement of the donor and acceptor moieties, expectedly gave only alpha-glycoside 36 alpha in very high yield. Thus, the efficiency and versatility of this conceptual approach to intramolecular glycoside bond formation is exhibited.

  DOI：

  10.1021/jo990132e

文献信息

• Efficient Intramolecular Glycosylation Supported by a Rigid Spacer
  作者：Matthias Müller、Ursula Huchel、Armin Geyer、Richard R. Schmidt

  DOI：10.1021/jo990132e

  日期：1999.8.1

  The m-xylylene moiety was employed as rigid spacer in intramolecular glycoside bond formation. Fifteen-membered macrocycle formation starting from 6-O-linked donor and 6- and 4-O-linked acceptor (5a,b, 6b) led exclusively to beta(1-4)- and beta(1-6)-linked compounds 7 beta and 8 beta, respectively, which gave cellobioside and gentiobioside derivatives. The glycosylation yields could be improved by 14-membered macrocycle formation. In the four cases studied, the donor was 6-O-linked to the spacer. For the acceptor linkage to the spacer and the accepting hydroxy group, relative D-/L-threo- and D-/L-erythro-arrangements were chosen. Standard glycosylation conditions led in three cases (13, 14, 23) only to beta-linkage in high yield (16 beta, 17 beta, 25 beta). For the transformation of 24, having a D-erythro-arrangement in the acceptor moiety, the alpha-anomer 26 alpha was preferentially obtained. Limitation of the conformational space of the donor and the acceptor as in 31, which is stereochemically identical with 24, led to the corresponding alpha-glycoside 32 alpha in 87% yield. Synthesis of a pseudo mirror image of 23 [having 6-(D)/3-(D-threo)-arrangement], namely 35, having 3(L)/6-(L-threo)-arrangement of the donor and acceptor moieties, expectedly gave only alpha-glycoside 36 alpha in very high yield. Thus, the efficiency and versatility of this conceptual approach to intramolecular glycoside bond formation is exhibited.