1-((2R,3R,4R,5S,6R)-2-Azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl)-propan-2-one | 857419-94-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-((2R,3R,4R,5S,6R)-2-Azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl)-propan-2-one
• 英文别名: 1-[(2R,3R,4R,5S,6R)-2-azido-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl]propan-2-one
• CAS: 857419-94-4
• 化学式: C₃₀H₃₃N₃O₅
• 分子量: 515.609
• InChiKey: LIIJNMPXKZCHTR-XZTOTZIXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  38
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  68.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-((2R,3R,4R,5S,6R)-2-Azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl)-propan-2-one 在 sodium tetrahydroborate 、 水 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 40.0h， 生成 2-methyl-4-(1',2',4'-tri-benzyloxy-3'-hydroxy-butyl)pyrrolidine
  参考文献：
  名称：

  来自2-C-乙酰甲基-糖基叠氮化物的C-支链吡咯烷。减少单糖开环形成的亚胺

  摘要：

  受保护的2-C-乙酰甲基-β-吡喃葡萄糖基叠氮化物衍生物1的还原产生了相应的β-葡萄糖基胺3。我们建议将β-糖基胺进行异构化处理，而不是形成一个构象应变的1,2-反式稠合的双环亚胺。无环亚胺（4），然后通过5-羟基分子内闭环。具有1，2-顺式构型的所得2-C-乙酰甲基-α-吡喃葡萄糖胺5立即以优异的产率转化为双环亚胺（2）。尝试使用硼氢化钠和氰基硼氢化钠选择性还原2的C = N双键未能产生双环胺6。相反，化合物6经历了另一个开环消除并进一步还原，从而以高收率产生了C支化的吡咯烷（8） 。

  DOI：

  10.1016/j.carres.2006.07.005
• 作为产物：
  描述：

  1′-C-acetyl-3,4,6-tri-O-benzyl-1,2-cyclopropane-1,2-deoxy-α-D-glucopyranose 在 sodium azide 作用下， 生成 1-((2R,3R,4R,5S,6R)-2-Azido-4,5-bis-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yl)-propan-2-one
  参考文献：
  名称：

  One-Pot Synthesis of 2-C-Branched Glycosyl Triazoles by Integrating 1,2-Cyclopropanated Sugar Ring-Opening Azidation and CuAAC Reaction

  摘要：

  DOI：

  10.1021/acs.joc.2c02390

文献信息

• 1,2-Migration of 2‘-Oxoalkyl Group and Concomitant Synthesis of 2-<i>C</i>-Branched <i>O</i>-, <i>S</i>-Glycosides and Glycosyl Azides via 1,2-Cyclopropanated Sugars
  作者：Huawu Shao、Sanchai Ekthawatchai、Chien-Sheng Chen、Shih-Hsiung Wu、Wei Zou

  DOI：10.1021/jo0502854

  日期：2005.6.1

  Treatment of 2'-oxoalkyl 2-O-Ms(Ts)-alpha-C-mannosides (4, 5, and 6) with base resulted in 1,2-cyclopropanation via an intramolecular S(N)2 reaction due to their 1,2-trans-diaxial configurations. The 1,2-cyclopropanated sugars (10 and 13) were reacted with various alcohols, thiols, and sodium azide to produce 2-C-branched O- and S-glycosides and glycosyl azides (11, 14-28) in good to excellent yields. In contrast, 1,2-cis 2'-oxoalkyl 2-O-Ms(Ts)-alpha-C-glucoside 9 formed an acyclic conjugated aldehyde (31) under basic conditions, which occurred by 1'-enolation followed by beta-elimination. An intramolecular Michael addition from 31 produced 2-O-Ms-beta-C-glucoside 30 as a major product. However, due to the electron-withdrawing effect exerted by 2-O-Ms compound 31 also undergoes a C2 epimerization to form 32. Thereafter, the intramolecular Michael addition led to the formation of both 1,2-trans 2'-oxoalkyl 2-O-Ms-alpha-C-mannoside 4 and its beta-anomer (33). Because beta-elimination/Michael addition and C2 epimerization are reversible reactions, equilibriums among 9, 31, 30, 32, 33, and 4 were established, which included the transformation of 1,2-cis C-glucoside 9 into 1,2-trans C-mannoside 4. The subsequent 1,2-cyclopropanation of 4 was an irreversible reaction yielding 1,2-cyclopropanated 10 and further conversion to 1,2-migration products (11 and 12).
• C-Branched pyrrolidines from 2-C-acetylmethyl-glycosylazides. Reduction of imines formed by monosaccharide ring opening
  作者：Huawu Shao、Dean T. Williams、Shih-Hsiung Wu、Wei Zou

  DOI：10.1016/j.carres.2006.07.005

  日期：2006.10

  conformationally strained 1,2-trans-fused bicyclic imine, we propose that the beta-glycosylamine underwent anomerization to an acyclic imine (4) followed by an intramolecular ring closure by the 5-hydroxy group. The resultant 2-C-acetylmethyl-alpha-glucopyranosylamine 5, which possesses the 1,2-cis-configuration was immediately converted to a bicyclic imine (2) in excellent yield. Attempts to selectively

  受保护的2-C-乙酰甲基-β-吡喃葡萄糖基叠氮化物衍生物1的还原产生了相应的β-葡萄糖基胺3。我们建议将β-糖基胺进行异构化处理，而不是形成一个构象应变的1,2-反式稠合的双环亚胺。无环亚胺（4），然后通过5-羟基分子内闭环。具有1，2-顺式构型的所得2-C-乙酰甲基-α-吡喃葡萄糖胺5立即以优异的产率转化为双环亚胺（2）。尝试使用硼氢化钠和氰基硼氢化钠选择性还原2的C = N双键未能产生双环胺6。相反，化合物6经历了另一个开环消除并进一步还原，从而以高收率产生了C支化的吡咯烷（8） 。
• One-Pot Synthesis of 2-<i>C</i>-Branched Glycosyl Triazoles by Integrating 1,2-Cyclopropanated Sugar Ring-Opening Azidation and CuAAC Reaction
  作者：Zhongke Shen、Qin Tang、Wei Jiao、Huawu Shao、Xiaofeng Ma

  DOI：10.1021/acs.joc.2c02390

  日期：2022.12.16