2-O-(Cyclohexylcarbamoyl)-6-O-formyl-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranosyl fluoride | 159493-46-6

• 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: 2-O-(Cyclohexylcarbamoyl)-6-O-formyl-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranosyl fluoride
• 英文别名: [(2S,3aR,4R,6R,7S,7aR)-7-(cyclohexylcarbamoyloxy)-6-fluoro-2-(trichloromethyl)-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methyl formate
• CAS: 159493-46-6
• 化学式: C₁₆H₂₁Cl₃FNO₇
• 分子量: 464.703
• InChiKey: JBTMQCYCBQZJGE-TVQXOTEMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  92.3
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2-O-(Cyclohexylcarbamoyl)-6-O-formyl-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranosyl fluoride 在 三氟化硼乙醚 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 48.0h， 以84%的产率得到Cyclohexyl-carbamic acid (1R,2R,4S,6R,7S,8R)-4-trichloromethyl-3,5,9,11-tetraoxa-tricyclo[6.2.1.0^2,6]undec-7-yl ester
  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：

  N,N'-二环己基碳二亚胺 在 氢氟酸 、 乙酸酐 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 14.5h， 生成 2-O-(Cyclohexylcarbamoyl)-6-O-formyl-3,4-O-(2,2,2-trichloroethylidene)-α-D-altropyranosyl fluoride
  参考文献：
  名称：

  Organofluorverbindungen und Fluorierungsagenzien 12¹. Vonmanno-Pyranosiden zu 3,4-O-(2,2,2-Trichlorethyliden)altropyranosylfluoriden in nur zwei Reaktionsschritten

  摘要：

  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。

  DOI：

  10.1055/s-1994-25583

文献信息

• New Stereospecific Rearrangements of Pyranosides
  作者：Ralf Miethchen、Daniel Rentsch、Michael Frank

  DOI：10.1080/07328309608005421

  日期：1996.1

  Methyl beta-D-arabinopyranoside (1), phenyl 1-thio-beta-D-galactopyranoside (3), methyl alpha-L-fucopyranoside (7), methyl beta-1-fucopyranoside (9), 1,6-anhydro-beta-D-galactopyranoside (D-galactosan; 11), and 1,6-anhydro-beta-D-mannopyranoside (D-mannosan; 14) were stereospecifically converted in moderate up to good yields into methyl 4-O-cyclohexylcarbamoyl-2,3-O-(2,2,2-trichloroethylidene)-beta-D-lyxopyranoside (2), phenyl 4-O-cyclohexylcarbamoyl-6-O-formyl-2,3-O-(2,2,2-trichloroethylidene)-1-thio-beta-D-gulopyranoside (4) / phenyl 4-O-cyclohexylcarbamoyl-2,3-O-(2,2,2-trichloroethylidene)-1-thio-beta-D-gulopyranoside (5), methyl 4-O-cyclohexylcarbamoyl-2,3-O-(2,2,2-trichloroethylidene)-6-deoxy-alpha-L-gulopyranoside (8), methyl 2,3-O-(2,2,2-trichloroethylidene)-4-O-cyclohexylcarbamoyl-6-deoxy-beta-L-gulopyranoside (10), 1,6-anhydro-4-O-cyclohexylcarbamoyl-2,3-O-(2,2,2-trichloroethylide)-beta-D-gulopyranoside (12), and 1,6-anhydro-2-O-cyclohexylcarbamoyl-3,4-O-(2,2,2-trichloroehtylidene)-beta-D-altropyranoside (15), respectively, using a nonclassic pathway of chloral acetalisation with dicyclohexylcarbodiimide (DCC) as coagent. In the case of 1, 3, and 9, chloral acetalisatiens yielded diastereomeric mixtures, e.g., the acetals 2, 4, 5, and 10 consist of endo-H/exo-H dioxolane type acetals with preference of the endo-H form. In contrast to this, the compounds 7, 11, and 14 gave exclusively the endo-H diastereomers 8, 12, and 15. Additionally, the structure of the anhydro compound 15 was confirmed by intramolecular glycosylation of the 2-O-cyclohexylcarbamoyl-3,4-O-(2,2,2-trichloroethylidene)-alpha-D-altropyranosyl fluoride (17). Finally, the 6-O-formyl-beta-D-gulopyranoside 4 was alternatively deformylated by methanol/triethylamine giving 5 and methanol/sodium methoxide yielding phenyl 6-O-cyclohexylcarbamoyl-2,3-O-(2,2,2-trichloroethylidene)-1-thio-beta-D-gulopyranoside (6). The carbamoyl protecting group of 12 was cleaved by refluxing with methanolic sodium methoxide solution giving 1,6-anhydro-2,3-O-(2,2,2-trichloroethylidene)-beta-D-gulopyranoside (13).
• Miethchen, Ralf; Rentsch, Daniel, Liebigs Annalen, 1996, # 4, p. 539 - 543
  作者：Miethchen, Ralf、Rentsch, Daniel

  DOI：——

  日期：——
• 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。