L-1-O-benzyl-6-O-cyclohexylcarbamoyl-2-O-methyl-4,5-O-trichloroethylidene-muco-inositol | 402724-04-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: L-1-O-benzyl-6-O-cyclohexylcarbamoyl-2-O-methyl-4,5-O-trichloroethylidene-muco-inositol
• 英文别名: [(2S,3aR,4R,5S,6S,7S,7aR)-7-hydroxy-6-methoxy-5-phenylmethoxy-2-(trichloromethyl)-3a,4,5,6,7,7a-hexahydro-1,3-benzodioxol-4-yl] N-cyclohexylcarbamate
• CAS: 402724-04-3
• 化学式: C₂₃H₃₀Cl₃NO₇
• 分子量: 538.853
• InChiKey: HELPOAZNWDPTLK-MCLWVUGISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  95.5
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  L-1-O-benzyl-6-O-cyclohexylcarbamoyl-2-O-methyl-4,5-O-trichloroethylidene-muco-inositol 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 16.0h， 以85%的产率得到L-1-O-benzyl-2-O-methyl-4,5-O-trichloroethylidene-muco-inositol
  参考文献：
  名称：

  Selective epimerization of l-chiro-inositol to l-muco- and d-chiro-inositol derivatives

  摘要：

  In a one step procedure, L-1-O-benzyl-2-O-methyl-chiro-inositol (1) was acetalized to the L-muco-inositol derivatives 2, 3 and D-2-O-benzyl-3-O-cyclohexylcarbamoyl-4-deoxy-4-(N,N'-dicyclohexylureido)-1-O-methyl-5,6-O-trichloroethylidene-chiro-inositol (4). Complete conversion of L-1-O-benzyl-6-O-cyclohexylcarbamoyl-3-O-formyl-2-O-mothyl-4,5-O-trichloroethylidene-muco-inositol (3) into L-1-O-benzyl-6-O-cyclohexylcarbamoyl-2-O-methyl-4,5-O-trichloroethylidene-muco-inositol (2) is feasible by deformylation in boiling methanolic triethylamine. Furthermore, stepwise deprotection of 2 and 4 is described. Thus, compounds 5, 10, and 7 were obtained by decarbamoylation of 2, 4, and 6, respectively, with boiling methanolic sodium methoxide. The trichloroethylidene group of L-1-O-benzyl-2-O-methyl-4,5-O-trichloroethylidene-muco-inositol (5) was removed in a two step procedure (hydrodechlorination-deacetalization) via the ethylidene acetal 7 to give L-1-O-benzyl-2-O-methyl-muco-inositol (9). On refluxing D-chiro-inositol derivative 4 with 99% acetic acid, the ureido moiety was cleaved generating D-2-O-benzyl-4-cyclo-hexylamino-3-O-cyclohexylcarbamoyl-4-deoxy-1-O-methyl-5,6-O-trichloroethylidene-chiro-inositol (11). By contrast, cleavage of the ureido moiety of 10 was relatively difficult. The corresponding D-2-O-benzyl-4-cyclohexylamino-4-deoxy-1-O-methyl-5,6-O-trichloroethylidene-chiro-inositol (12) was only formed in small amounts. The structures of 1, 3 and 10 were confirmed by X-ray analysis. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00281-6
• 作为产物：
  描述：

  L-1-O-benzyl-6-O-cyclohexylcarbamoyl-3-O-formyl-2-O-methyl-4,5-O-trichloroethylidene-muco-inositol 在 三乙胺 作用下， 以 甲醇 为溶剂， 反应 0.25h， 以100%的产率得到L-1-O-benzyl-6-O-cyclohexylcarbamoyl-2-O-methyl-4,5-O-trichloroethylidene-muco-inositol
  参考文献：
  名称：

  由左旋手性前体意外形成右旋手性肌醇

  摘要：

  在一步法工艺，使用1-1 -O-苄基-2 - O-甲基-手性肌醇（1）中的缩醛化的1-粘膜肌醇衍生物2，3和d-2- ø -苄基-3- - ö -cyclohexylcarbamoyl -4-（N，N'-脲基）-4-脱氧-1 -O-甲基-5,6- -O- trichloroethylidene-手性肌醇（4）。1-1- O-苄基-6- O-环己基氨基甲酰基-3- O-甲酰基-2- O-甲基-4,5- O-三氯亚乙基-粘膜肌醇（3）定量deformylated到L-1 -O-苄基-6- -O-环己基-2- -O-甲基-4,5- -O- trichloroethylidene-粘膜肌醇（2）通过煮沸甲醇三乙胺。

  DOI：

  10.1016/s0040-4039(01)01899-8

文献信息

• Concentrated hydriodic acid in simultaneous deprotections of multifunctional inositols
  作者：Ralf Miethchen、Andreas Schmidt、Katharina Neitzel、Manfred Michalik、Thomas Pundt、Wolfgang Ruth

  DOI：10.1016/j.carres.2004.11.031

  日期：2005.3

  L-1-Deoxy-1-fluoro-6-O-methyl-myo-inositol was epimerized by chloral/DCC in boiling 1,2-dichloroethane yielding D-1-O-cyclohexylcarbaramoyl-2-deoxy-2-fluoro-3-O-methyl-5,6-O-[(R/S)-2,2,2-trichloroethylidene]-chiro-inositol. The latter and L-4-O-benzyl-3-O-cyclohexylcarbamoyl-5-O-methyl-1,2-O-(2,2,2-trichloroethylidene)-muco-inositol, L-4-O-benzyl-3-O-cyclohexylcarbamoyl-1,2-O-ethylidene-5-O-methyl-chiro-inositol, D-1-O-cyclohexylcarbamoyl-2-deoxy-5,6-O-ethylidene-2-fluoro-3-O-methyl-chiro-inositol, as well as D-5-O-benzyl-4-O-cyclohexylcarbamoyl-3-deoxy-3-(N,N'-dicyclohexylureido)-6-O-methyl-1,2-O-(2,2,2-trichloroethylidene)-chiro-inositol were deprotected with boiling 57% aq hydrogen iodide. Ether, urethane and ethylidene acetal functions were simultaneously cleaved by the reagent, whereas the trichloroethylidene groups were still intact or were only removed ill small quantities. Especially, the urea function of D-5-O-benzyl-4-O-cyclohexylcarbamoyl-3-deoxy-3-(N,N'-dicyclohexylureido)-6-O-methyl-1,2-O-(2,2,2-trichloroethylidene)-chiro-inositol was decomposed to a cyclohexylamino, group. The hydrodechlorination of D-1-O-cyclohexylcarbamoyl-2-deoxy-2-fluoro-3-O-methyl-5,6-O-[(R/S)-2,2,2-trichloroethylidene]-chiro-inositol using Raney-Nickel yielded a mixture of the corresponding 5,6-O-ethylidene- and 5,6-O-chloroethylidene derivatives. The three synthetic steps-hydrodehalogenation, HI-deprotection and peracylation- were combined without purification of the intermediates. (c) 2005 Elsevier Ltd. All rights reserved.