methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido-β-D-allopyranoside | 1300080-70-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido-β-D-allopyranoside
• 英文别名: 1-[(2R,3R,4S,5S,6R)-4,5-dihydroxy-2-methoxy-6-(phenylmethoxymethyl)oxan-3-yl]-3,4-dimethylpyrrole-2,5-dione
• CAS: 1300080-70-9
• 化学式: C₂₀H₂₅NO₇
• 分子量: 391.421
• InChiKey: LVHPIONMQRUHJX-XFEYQPKCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  106
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido-β-D-allopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 四丁基氟化铵 、 溶剂黄146 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 18.42h， 生成 methyl 2,3,4-tri-O-acetyl-6-O-benzyl-β-D-glucopyranosyl-(1→4)-3-O-acetyl-6-O-benzyl-2-deoxy-2-dimethylmaleimido-β-D-allopyranoside
  参考文献：
  名称：

  Differential O-3/O-4 selectivity in the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors: effect of a conformationally armed (superarmed) glycosyl donor

  摘要：

  An assessment of the relative O-3/O-4 reactivities of both alpha- and beta-methyl glycosides of N-dimethylmaleoyl (DMM) glucosamine and allosamine acceptors protected at O-6 with a benzyl group using a D-glucopyranosyl conformationally armed donor (superarmed donor) counterpart is presented. The glycosylation of glucosamine derivatives followed the trends already observed for disarmed donors. On the other hand, the glycosylation of allosamine derivatives gave exclusively substitution on the equatorial O-4, in spite that with a disarmed donor the point of substitution is exclusively on the more hindered, electronically-preferred O-3. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2013.08.002
• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-2-deoxy-2-dimethylmaleimido-β-D-allopyranoside 在 硼烷-三甲胺络合物 、 三氟化硼乙醚 作用下， 以 乙腈 为溶剂， 反应 1.5h， 以72%的产率得到methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido-β-D-allopyranoside
  参考文献：
  名称：

  Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach

  摘要：

  当与全乙酰化 α-D-吡喃半乳糖的三氯乙酰亚胺酯 (5) 反应时，6-O-苄基-N-二甲基马来酰基-D-别糖胺的甲基糖苷的两个端基异构体（6 和 7）仅在 O3 上糖基化。 6（α-端基异构体）预计具有区域选择性，因为其 H(O)3 与二甲基马来酰基的羰基发生强氢键，如 NMR 温度依赖性所示。然而，对于 7（β-端基异构体）来说，实验中并没有遇到这种氢键。对糖基化反应带电中间体类似物中隐含能量的 DFT 研究已经根据这些带电中间体上发生的强氢键巧妙地解释了这种行为。这种方法解释了 6 和 7 的实验区域选择性，但此外，计算显示与文献中其他相关化合物的区域选择性明显一致。

  DOI：

  10.1039/c1ob00021g

文献信息

• Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach
  作者：María I. Colombo、Edmundo A. Rúveda、Carlos A. Stortz

  DOI：10.1039/c1ob00021g

  日期：——

  Both anomers of the methyl glycoside of 6-O-benzyl-N-dimethylmaleoyl-D-allosamine (6 and 7) are glycosylated exclusively on O3 when reacting with the trichloroacetimidate of peracetylated α-D-galactopyranose (5). This regioselectivity is expected for 6, the α-anomer, as a strong hydrogen bond of its H(O)3 with the carbonyl group of the dimethylmaleoyl group occurs, as shown by NMR temperature dependence. However, this hydrogen bond was not encountered experimentally for 7, the β-anomer. A DFT study of the energies implied in an analog of the glycosylation reaction charged intermediate has explained neatly this behavior, in terms of strong hydrogen bonds occurring at these charged intermediates. This approach explains both the experimental regioselectivities found for 6 and 7, but furthermore the calculations have shown a marked agreement with the regioselectivities found for other related compounds in the literature.

  当与全乙酰化 α-D-吡喃半乳糖的三氯乙酰亚胺酯 (5) 反应时，6-O-苄基-N-二甲基马来酰基-D-别糖胺的甲基糖苷的两个端基异构体（6 和 7）仅在 O3 上糖基化。 6（α-端基异构体）预计具有区域选择性，因为其 H(O)3 与二甲基马来酰基的羰基发生强氢键，如 NMR 温度依赖性所示。然而，对于 7（β-端基异构体）来说，实验中并没有遇到这种氢键。对糖基化反应带电中间体类似物中隐含能量的 DFT 研究已经根据这些带电中间体上发生的强氢键巧妙地解释了这种行为。这种方法解释了 6 和 7 的实验区域选择性，但此外，计算显示与文献中其他相关化合物的区域选择性明显一致。
• Differential O-3/O-4 selectivity in the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors: effect of a conformationally armed (superarmed) glycosyl donor
  作者：F. Della Felice、Edmundo A. Rúveda、Carlos A. Stortz、María I. Colombo

  DOI：10.1016/j.carres.2013.08.002

  日期：2013.10

  An assessment of the relative O-3/O-4 reactivities of both alpha- and beta-methyl glycosides of N-dimethylmaleoyl (DMM) glucosamine and allosamine acceptors protected at O-6 with a benzyl group using a D-glucopyranosyl conformationally armed donor (superarmed donor) counterpart is presented. The glycosylation of glucosamine derivatives followed the trends already observed for disarmed donors. On the other hand, the glycosylation of allosamine derivatives gave exclusively substitution on the equatorial O-4, in spite that with a disarmed donor the point of substitution is exclusively on the more hindered, electronically-preferred O-3. (C) 2013 Elsevier Ltd. All rights reserved.