methyl 2,6-di-O-benzyl-3-O-(4-methoxybenzyl)-α-D-galactopyranoside | 241470-97-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,6-di-O-benzyl-3-O-(4-methoxybenzyl)-α-D-galactopyranoside
• 英文别名: methyl 2,6-di-O-benzoyl-3-O-methoxyphenylmethyl-α-D-galactopyranoside；Bn(-2)[Mob(-3)][Bn(-6)]a-Gal1Me；(2R,3S,4S,5R,6S)-6-methoxy-4-[(4-methoxyphenyl)methoxy]-5-phenylmethoxy-2-(phenylmethoxymethyl)oxan-3-ol
• CAS: 241470-97-3
• 化学式: C₂₉H₃₄O₇
• 分子量: 494.585
• InChiKey: FYKUWCCCSHUYMP-LLQHYSMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  75.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 2,6-di-O-benzyl-3-O-(4-methoxybenzyl)-α-D-galactopyranoside 在 N-碘代丁二酰亚胺 、 三氟甲磺酸 、 sodium hydride 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.5h， 生成 methyl 4,6'-O-(1,3-xylylene)-(2,3,4-tri-O-benzyl-β-D-glucopyranosyl)-(1'->3)-2,6-di-O-benzyl-α-D-galactopyranoside
  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：

  (2R,3R,4S,5R,6S)-5-Benzyloxy-2-benzyloxymethyl-6-methoxy-tetrahydro-pyran-3,4-diol 、 4-甲氧基氯苄 在 二正丁基氧化锡 、 四丁基碘化铵 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以72%的产率得到methyl 2,6-di-O-benzyl-3-O-(4-methoxybenzyl)-α-D-galactopyranoside
  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

• Synthesis of Trisaccharides and Tetrasaccharides by Means of Intramolecular Glycosylation Supported by Rigid Spacers
  作者：Matthias Müller、Richard R. Schmidt

  DOI：10.1002/1099-0690(200106)2001:11<2055::aid-ejoc2055>3.0.co;2-n

  日期：2001.6

  4-O-unprotected galactoside derivative 6 as acceptor, afforded β-linked macrocyclic trisaccharide 9β in high yield after removal of the 3-O-MPM protective group and subsequent intramolecular glycoside bond formation. Similarly, by the same sequence of steps, the corresponding tetrasaccharide 14β was obtained from 5 and 4b-O-unprotected lactoside 11. For reiterative glycoside bond formation, treatment of α,α

  用 6-O-未保护的硫代麦芽糖苷 4 作为糖基供体 (5)，然后用 4-O-未保护的半乳糖苷衍生物 6 作为受体处理 α,α'-二溴-间二甲苯，以高产率得到 β-连接的大环三糖 9β在去除 3-O-MPM 保护基团和随后的分子内糖苷键形成后。类似地，通过相同的步骤顺序，从 5 和 4b-O-未保护的乳糖苷 11 中获得相应的四糖 14β。对于重复糖苷键的形成，用 3-O-未保护的 α,α'-二溴-间二甲苯处理硫糖苷 15 作为供体 (16)，然后是 4,6-O-未保护的葡糖苷，随后糖基化得到大环麦芽三糖苷 22，将其转化为已知的麦芽三糖苷 23。