Methyl 6-O-formyl-2-O-(cyclohexylcarbamoyl)-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranoside | 159493-45-5

• 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: Methyl 6-O-formyl-2-O-(cyclohexylcarbamoyl)-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranoside
• 英文别名: Methyl-2-O-(cyclohexylcarbamoyl)-6-O-formyl-3,4-O-(2,2,2-trichlorethyliden)-α-D-altropyranosid；[(2S,3aR,4R,6S,7S,7aR)-7-(cyclohexylcarbamoyloxy)-6-methoxy-2-(trichloromethyl)-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methyl formate
• CAS: 159493-45-5
• 化学式: C₁₇H₂₄Cl₃NO₈
• 分子量: 476.738
• InChiKey: CXBBSQJAZXKFHM-JNWWKETESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  102
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Methyl 6-O-formyl-2-O-(cyclohexylcarbamoyl)-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranoside 在 三乙胺 作用下， 以 甲醇 为溶剂， 反应 0.17h， 生成 Methyl 2-O-(Cyclohexylcarbamoyl)-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranoside
  参考文献：
  名称：

  Miethchen, Ralf; Rentsch, Daniel, Liebigs Annalen, 1996, # 4, p. 539 - 543

  摘要：

  DOI：
• 作为产物：
  描述：

  三氯乙醛 、 N,N'-二环己基碳二亚胺 、 甲基-D-丙噻 以 1,2-二氯乙烷 为溶剂， 反应 4.5h， 生成 Methyl 6-O-formyl-2-O-(cyclohexylcarbamoyl)-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranoside
  参考文献：
  名称：

  Chloral/DCC - reagent for stereospecific rearrangements and new protecting group techniques in carbohydrate chemistry

  摘要：

  DOI：

  10.1002/prac.19953370191

文献信息

• Organofluorverbindungen und Fluorierungsagenzien 12¹. Von<i>manno</i>-Pyranosiden zu 3,4-<i>O</i>-(2,2,2-Trichlorethyliden)altropyranosylfluoriden in nur zwei Reaktionsschritten
  作者：Ralf Miethchen、Daniel Rentsch

  DOI：10.1055/s-1994-25583

  日期：——

  Organofluorine Compounds and Fluorinating Agents 12.1 From manno-Pyranosides to 3,4-O-(2,2,2-Trichloroethylidene) altropyranosyl Fluorides in Only Two Reaction Steps Methyl α-D-mannopyranoside (1) and methyl α-L-rhamnopyrano-side (9) react with chloral and dicyclohexylcarbodiimide (DCC) in an one-pot reaction selectively to form the α-D-altropyranoside 2 and α-L-altropyranoside 10, respectively, in good yield. The glycosyl donor 3 was prepared from 2 by treatment with hydrogen fluoride/nitromethane/acetic anhydride. Compound 2 can be deprotected stepwise by treatment with methanol/sodium methanolate at r.t. to 4, and heating under reflux to methyl 3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranoside (5). Treatment of the dihydroxy derivative 5 with hydrogen fluoride/nitromethane/acetic anhydride gave an anomeric mixture of the α/β-D-altropyranosyl fluorides 6. Acylation of 5 with benzoyl or pivaloyl chloride gave the corresponding 2,6-diacyl derivatives 7 and 8, respectively. Finally, the α-L-altro-pyranoside 10 was deprotected in boiling methanol/sodium methanolate to afford the α-L-altropyranoside 11 and fluorinated in hydrogenfluoride/nitromethane/acetic anhydride to α-L-altropyranosyl fluoride 12. The various functionalized altropyranoses differ partially in their conformations. The ratio of the endo-H to exo-H diastereomers of the chloral acetals was determined.

  有机氟化合物和氟化剂 12.1 从甘露吡喃糖苷到 3,4-O-(2,2、甲基δ-D-吡喃甘露糖苷 (1) 和甲基δ-L-吡喃鼠李糖苷 (9) 与氯醛和二环己基碳二亚胺 (DCC) 发生选择性反应，分别生成δ-D-吡喃金刚烷糖苷 2 和δ-L-吡喃金刚烷糖苷 10，产率良好。用氟化氢/硝基甲烷/乙酸酐处理 2，制备出糖基供体 3。将化合物 2 用甲醇/甲醇钠在恒温条件下处理至 4，然后在回流条件下加热，可逐步脱保护，制得甲基 3,4-O-(2,2,2-三氯亚乙基)-δ±-D-酰基吡喃糖苷 (5)。 用氟化氢/硝基甲烷/乙酸酐处理二羟基衍生物 5，得到δ/δ-D-altropyranosyl 氟化物 6 的同分异构体混合物。用苯甲酰氯或特戊酰氯对 5 进行酰化，分别得到相应的 2,6-二乙酰基衍生物 7 和 8。最后，δ-L-酰基吡喃糖苷 10 在沸腾的甲醇/甲醇钠中脱保护，得到δ-L-酰基吡喃糖苷 11，在氟化氢/硝基甲烷/乙酸酐中氟化，得到δ-L-酰基吡喃糖基氟化物 12。各种官能化的altropyranoses在构象上存在部分差异。测定了氯醛缩醛的内-H 非对映异构体和外-H 非对映异构体的比例。