4,6-di-O-acetyl-3-O-carbamoyl-D-glucal | 1133981-89-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 4,6-di-O-acetyl-3-O-carbamoyl-D-glucal
• 英文别名: 3O-carbamoyl-4,6-di-O-acetyl-D-glucal；[(2R,3S,4R)-3-acetyloxy-4-carbamoyloxy-3,4-dihydro-2H-pyran-2-yl]methyl acetate
• CAS: 1133981-89-1
• 化学式: C₁₁H₁₅NO₇
• 分子量: 273.243
• InChiKey: REMNCFQJTGFVPF-BBBLOLIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  114
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  4,6-di-O-acetyl-3-O-carbamoyl-D-glucal 、 叔丁醇 在 dirhodium tetraacetate 、 二(叔丁基羰基氧基)碘苯 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以83%的产率得到((3aS,4R,6R,7S,7aR)-7-acetoxy-4-(tert-butoxy)-2-oxohexahydro-4H-pyrano[3,4-d]oxazol-6-yl)methyl acetate
  参考文献：
  名称：

  New chemo-enzymatic route toward N-acetylneuraminic acid derivatives with alkyl groups at C-7 hydroxyl group

  摘要：

  Based on chemo-enzymatic regio- and stereoselective reactions, new routes toward C-4 substituted N-acetyl-D-mannosamine (ManNAc) and the corresponding sialic acids from D-glucal were established. Lipase-catalyzed regioselective transformation of n-glucal and related substrates furnished precursors on which carbamate and alkyl substituent were properly introduced at C-3 and at C-4, respectively. Cyclic carbamate formation through rhodium-nitrenoid intermediates with iodobenzene pivalate and tertbutyl alcohol proceeded in manna-configured at C-2 as well as alpha- at C-1, exclusively. Ring opening and deprotection under mild conditions furnished the target ManNAc derivatives, which were the substrates for aldolase-catalyzed reactions. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.04.045
• 作为产物：
  描述：

  在 aluminum oxide 、 水 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以1 g的产率得到4,6-di-O-acetyl-3-O-carbamoyl-D-glucal
  参考文献：
  名称：

  New chemo-enzymatic route toward N-acetylneuraminic acid derivatives with alkyl groups at C-7 hydroxyl group

  摘要：

  Based on chemo-enzymatic regio- and stereoselective reactions, new routes toward C-4 substituted N-acetyl-D-mannosamine (ManNAc) and the corresponding sialic acids from D-glucal were established. Lipase-catalyzed regioselective transformation of n-glucal and related substrates furnished precursors on which carbamate and alkyl substituent were properly introduced at C-3 and at C-4, respectively. Cyclic carbamate formation through rhodium-nitrenoid intermediates with iodobenzene pivalate and tertbutyl alcohol proceeded in manna-configured at C-2 as well as alpha- at C-1, exclusively. Ring opening and deprotection under mild conditions furnished the target ManNAc derivatives, which were the substrates for aldolase-catalyzed reactions. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.04.045

文献信息

• Protecting Group and Solvent Control of Stereo- and Chemoselectivity in Glucal 3-Carbamate Amidoglycosylation
  作者：Ritu Gupta、Kimberly M. Sogi、Sarah E. Bernard、John D. Decatur、Christian M. Rojas

  DOI：10.1021/ol900126q

  日期：2009.4.2

  In the Rh-2(OAC)(4)-catalyzed amidoglycosylation of glucal 3-carbamates, anomeric stereoselectivity and the extent of competing C3-H oxidation depend on the 40 and 60 protecting groups. Acyclic protection permits high alpha-anomer selectivity with further improvement in less polar solvents, while electron-withdrawing protecting groups limit C3-oxidized byproducts. Stereocontrol and bifurcation between alkene insertion and C3-H oxidation reflect an interplay of conformational, stereoelectronic, and inductive factors.