[(3aR,4R,7R,7aR)-7-azido-2,2-dimethyl-6-(4-methylphenyl)sulfanyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methanol | 1310050-46-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: [(3aR,4R,7R,7aR)-7-azido-2,2-dimethyl-6-(4-methylphenyl)sulfanyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methanol
• CAS: 1310050-46-4
• 化学式: C₁₆H₂₁N₃O₄S
• 分子量: 351.426
• InChiKey: BWGCKVFAOKVSRA-HHHGZCDHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  87.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [(3aR,4R,7R,7aR)-7-azido-2,2-dimethyl-6-(4-methylphenyl)sulfanyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methanol 在 N-溴代丁二酰亚胺(NBS) 、 水 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三氟乙酸 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 mineral oil 为溶剂， 反应 3.67h， 生成 3,4-di-O-acetyl-2-azido-6-O-benzyl-2-deoxy-α-D-galactopyranose 1-O-trichloroacetimidate
  参考文献：
  名称：

  Study of the Stereoselectivity of 2-Azido-2-deoxygalactosyl Donors: Remote Protecting Group Effects and Temperature Dependency

  摘要：

  The stereoselectivity of glycosylation reactions is affected by many factors. Synthesis of 1,2-cis glycosidic linkages (such as a linkages in glucose and galactose like monosaccharides) is challenging due to lack of control of the stereoselectivity. Our systematic study of GalN(3) donors with different combination of protecting groups indicated that acetyl groups at the 3- and 4-positions are particularly important for high alpha-selectivity. Temperature is also recognized as a major factor in control of stereoselectivity. Mechanisms responsible for these experimental results are discussed and explored using computational methods. A remote participation model of the acetyl groups is proposed to explain the directing effects of the acetyl groups.

  DOI：

  10.1021/jo1025157
• 作为产物：
  描述：

  p-methylphenyl 2-deoxy-2-azido-3,4,6-tri-O-acetyl-1-thio-D-galactopyranoside 在 camphor-10-sulfonic acid 、 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 24.5h， 生成 [(3aR,4R,7R,7aR)-7-azido-2,2-dimethyl-6-(4-methylphenyl)sulfanyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methanol
  参考文献：
  名称：

  Study of the Stereoselectivity of 2-Azido-2-deoxygalactosyl Donors: Remote Protecting Group Effects and Temperature Dependency

  摘要：

  The stereoselectivity of glycosylation reactions is affected by many factors. Synthesis of 1,2-cis glycosidic linkages (such as a linkages in glucose and galactose like monosaccharides) is challenging due to lack of control of the stereoselectivity. Our systematic study of GalN(3) donors with different combination of protecting groups indicated that acetyl groups at the 3- and 4-positions are particularly important for high alpha-selectivity. Temperature is also recognized as a major factor in control of stereoselectivity. Mechanisms responsible for these experimental results are discussed and explored using computational methods. A remote participation model of the acetyl groups is proposed to explain the directing effects of the acetyl groups.

  DOI：

  10.1021/jo1025157

文献信息

• 4,6-Di-O-Benzylidenyl group-directed preparation of 2-deoxy-2-azido-α-d-galactopyranosides promoted by 3-O-TBDPS
  作者：Xing-Yong Liang、Jing Yang、Zhong-Hao Qiu、Lei Wang、Todd L. Lowary、Hua-Jun Shawn Fan

  DOI：10.1016/j.carres.2021.108237

  日期：2021.2

  In this study, we designed a method to prepare 2-deoxy-2-azido-α-d-galactopyranosidic bonds using 4,6-di-O-benzylidenyl-3-O-t-butyldiphenylsilyl protected 2-deoxy-2-azido-1-thio-d-galactopyranoside 5 as donors. The donor 5 gives a good to excellent α-selectivity in the glycosylation with secondary alcohols, which was found to be associated with the benzylidenyl on 4,6-di-O and TBDPS on 3-O of the donor

  在这项研究中，我们设计了一种使用4,6-二-O-苄叉基-3-叔丁基二苯基甲硅烷基保护的2-脱氧-2-叠氮基-1制备2-脱氧-2-叠氮基-α-d-吡喃半乳糖苷键的方法。 -硫代-d-吡喃半乳糖苷5作为供体。供体5在与仲醇的糖基化中具有良好的优异的α-选择性，这与供体5的4，6-二-O上的亚苄基和3-O上的TBDPS有关。供体6和7，3-O-TBDPS可以增加硫糖苷的活性，而4,6-二-O-苄基上的孤对增强了gg-协同作用，这在提高立体选择性方面发挥了作用。最后，通过合成含α-半乳糖胺的五糖26证明了该方法。