(-)-menthyl 2-amino-2-N,3-O-carbonyl-2-deoxy-4,6-O-isopropylidene-2-N-(2,2,2-trichloroethoxycarbonyl)-α-D-mannopyranoside

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (-)-menthyl 2-amino-2-N,3-O-carbonyl-2-deoxy-4,6-O-isopropylidene-2-N-(2,2,2-trichloroethoxycarbonyl)-α-D-mannopyranoside
• 英文别名: 2,2,2-trichloroethyl (1S,2R,6S,7S,9R)-12,12-dimethyl-7-[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]oxy-4-oxo-3,8,11,13-tetraoxa-5-azatricyclo[7.4.0.02,6]tridecane-5-carboxylate
• 化学式: C₂₃H₃₄Cl₃NO₈
• 分子量: 558.884
• InChiKey: ISJJZWRKQALURK-MXHGJZDWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  35
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  92.8
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  4,6-O-异亚丙基-D-葡萄糖醛 在 dirhodium tetraacetate 4-二甲氨基吡啶 、 iodonium(di-γ-collidine) perchlorate 、 亚碘酰苯 、 4 A molecular sieve 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 25.0h， 生成 (-)-menthyl 2-amino-2-N,3-O-carbonyl-2-deoxy-4,6-O-isopropylidene-2-N-(2,2,2-trichloroethoxycarbonyl)-α-D-mannopyranoside
  参考文献：
  名称：

  α-N-Acetylmannosamine (ManNAc) Synthesis via Rhodium(II)-Catalyzed Oxidative Cyclization of Glucal 3-Carbamates

  摘要：

  Glucal 3-carbamates 1 and 7 underwent oxidative cyclization with iodobenzene diacetate or iodosobenzene in the presence of Rh-2(OAc)(4), providing mannosamine 2-N,3-O-oxazolidinones. With iodosobenzene, incorporation of 4-penten-1-ol provided a readily separable anomeric mixture of n-pentenyl glycosides, with the anomers exhibiting pronounced differences in reactivity as glycosyl donors. N-acylation of the sugar oxazolidinones led to a-selective glycosyl donors for the elaboration of various 2-mannosamine frameworks. Alternatively, the anomeric n-pentenyl glycosides of N-Cbz 2-mannosamine oxazolidinones were converted separately to oxazolidinone-opened derivatives 28 alpha and 28 beta. These served as stereoconvergent glycosyl donors, and the a-linked products were readily advanced to a variety of N-acetylmannosamine (ManNAc) frameworks, using an intramolecular O -> N acetyl transfer as the final step.

  DOI：

  10.1021/jo0500129

文献信息

• α-<i>N-</i>Acetylmannosamine (ManNAc) Synthesis via Rhodium(II)-Catalyzed Oxidative Cyclization of Glucal 3-Carbamates
  作者：Rena Bodner、Bridget K. Marcellino、Alexandra Severino、Abigail L. Smenton、Christian M. Rojas

  DOI：10.1021/jo0500129

  日期：2005.5.1

  Glucal 3-carbamates 1 and 7 underwent oxidative cyclization with iodobenzene diacetate or iodosobenzene in the presence of Rh-2(OAc)(4), providing mannosamine 2-N,3-O-oxazolidinones. With iodosobenzene, incorporation of 4-penten-1-ol provided a readily separable anomeric mixture of n-pentenyl glycosides, with the anomers exhibiting pronounced differences in reactivity as glycosyl donors. N-acylation of the sugar oxazolidinones led to a-selective glycosyl donors for the elaboration of various 2-mannosamine frameworks. Alternatively, the anomeric n-pentenyl glycosides of N-Cbz 2-mannosamine oxazolidinones were converted separately to oxazolidinone-opened derivatives 28 alpha and 28 beta. These served as stereoconvergent glycosyl donors, and the a-linked products were readily advanced to a variety of N-acetylmannosamine (ManNAc) frameworks, using an intramolecular O -> N acetyl transfer as the final step.