[(4S,5R)-2,2-dimethyl-5-[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]-1,3-dioxolan-4-yl]methanol | 177421-51-1

• 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: [(4S,5R)-2,2-dimethyl-5-[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]-1,3-dioxolan-4-yl]methanol
• CAS: 177421-51-1
• 化学式: C₁₇H₂₈O₈
• 分子量: 360.405
• InChiKey: TYRFSVLXABMDCR-VIFIDASRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  25
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  84.8
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [(4S,5R)-2,2-dimethyl-5-[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]-1,3-dioxolan-4-yl]methanol 在 吡啶 、 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 35.0h， 生成 (3aS,5aR,8aR,8bS)-3a-((4R,5S)-5-Azidomethyl-2,2-dimethyl-[1,3]dioxolan-4-yl)-2,2,7,7-tetramethyl-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran
  参考文献：
  名称：

  A new and highly stereoselective synthesis of polyhydroxyindolizidines from 4-octulose derivatives

  摘要：

  (1S,2S,6R,7R,8R,8aR)-1,2,6,7,8-五羟基吲哚齐啶（12）和(1R,6R,7R,8R,8aR)-1,6,7,8-四羟基吲哚齐啶（1,6-去环化合欢啶，24）已从重要关键中间体1,4-去氧-1,4-亚胺基-D-赤-L-阿洛-octitol（7）和1,2,4-三去氧-1,4-亚胺基-D-甘露糖基-D-塔罗-octitol（20）中以三步法立体选择性地合成。化合物7和20分别以四步法从2,3:4,5:6,7-三-O-异丙叉基-D-甘露糖基-D-半乳糖-oct-4-ulo-4,8-吡喃糖（1）和2-deoxy-4,5:6,7-二-O-异丙叉基-D-甘露糖-oct-4-ulo-4,8-吡喃糖（13）中容易获得。版权：1998 Elsevier Science Ltd. 保留所有权利。

  DOI：

  10.1016/s0957-4166(98)00064-0
• 作为产物：
  描述：

  果糖二丙酮 在 四氧化锇 、 lithium aluminium tetrahydride 、 potassium chlorate 、 4 A molecular sieve 、 对甲苯磺酸 、 copper(II) sulfate 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 丙酮 为溶剂， 反应 6.0h， 生成 [(4S,5R)-2,2-dimethyl-5-[(1R,2S,6S,9R)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-6-yl]-1,3-dioxolan-4-yl]methanol
  参考文献：
  名称：

  Synthesis of 4-Octuloses from a Derivative ofd-Fructose

  摘要：

  Reaction of 2,3:4,5-di-O-isopropylidene-beta-D-arabino-hexos-2-ulo-2,6-pyranose (1) with (methoxycarbonylmethylene)triphenylphosphorane in either dichloromethane or methanol gave methyl (E)-2,3-dideoxy-4,5:6,7-di-O-isopropylidene-beta-D-arabino-oct-2-ene-4-ulo-4,8-pyranosonate (2) or a 1:2.3 mixture of 2 and its Z-isomer (3), respectively. Bishydroxylation of 2 with osmium tetraoxide gave a mixture of methyl 4,5:6,7-di-O-isopropylidene-beta-D-glycero-D-galacto- (4) and -D-glycero-D-ido-oct-4-ulo-4,8-pyranosonate (5) which were carefully resolved by column chromatography. Compound 4 was transformed into its 2,3-di-O-methyl derivative (6) which was deacetonated to 7 and subsequently degraded to dimethyl 2,3-di-O-methyl-(+/-)-L-tartrate (8). On the other hand, acetonation of a mixture of 4 and 5 gave the corresponding tri-O-isopropylidene derivatives (9) and (10). Compounds 4 and 5 were reduced with LiAlH4 to the related 4,5:6,7-di-O-isopropylidene-beta-D-glycero-D-galacto- (11) and -beta-D-glycero-D-ido-oct-4-ulo-4,8-pyranose (12). Treatment of 11 and 12 with acetone/PTSA/CuSO4 only produced the acetonation at the C-2,3 positions. Finally, compounds 11 and 12 were deacetonated to the corresponding D-glycero-D-galacto- (15) and D-glycero-D-ido-oct-4-ulose (16).

  DOI：

  10.1080/07328309608005655

文献信息

• A new and highly stereoselective synthesis of polyhydroxyindolizidines from 4-octulose derivatives
  作者：Isidoro Izquierdo、Maria T Plaza、Rafael Robles、Antonio J Mota

  DOI：10.1016/s0957-4166(98)00064-0

  日期：1998.3

  (1S,2S,6R,7R,8R,8aR)-1,2,6,7,8-Pentahydroxyindolizidine 12 and (1R,6R,7R,8R,8aR)-1,6,7,8-tetrahydroxyindolizidine (1,6-diepicastanospermine, 24) have been stereoselectively synthesized from the important key intermediates 1,4-dideoxy-1,4-imino-D-erythro-L-altro-octitol 7 and 1,2,4-trideoxy-1,4-imino-D-glycero-D-talo-octitol 20 in three steps. Compounds 7 and 20 were readily obtained from 2,3:4,5:6,7-tri-O-isopropylidene-beta-D-glycero-D-galacto-oct-4-ulo-4,8-pyranose 1 and 2-deoxy-4,5:6,7-di-O-isopropylidene-beta-D-manno-oct-4-ulo-4,8-pyranose 13 in four steps, respectively. (C) 1998 Elsevier Science Ltd. All rights reserved.

  (1S,2S,6R,7R,8R,8aR)-1,2,6,7,8-五羟基吲哚齐啶（12）和(1R,6R,7R,8R,8aR)-1,6,7,8-四羟基吲哚齐啶（1,6-去环化合欢啶，24）已从重要关键中间体1,4-去氧-1,4-亚胺基-D-赤-L-阿洛-octitol（7）和1,2,4-三去氧-1,4-亚胺基-D-甘露糖基-D-塔罗-octitol（20）中以三步法立体选择性地合成。化合物7和20分别以四步法从2,3:4,5:6,7-三-O-异丙叉基-D-甘露糖基-D-半乳糖-oct-4-ulo-4,8-吡喃糖（1）和2-deoxy-4,5:6,7-二-O-异丙叉基-D-甘露糖-oct-4-ulo-4,8-吡喃糖（13）中容易获得。版权：1998 Elsevier Science Ltd. 保留所有权利。
• Synthesis of 4-Octuloses from a Derivative of<scp>d</scp>-Fructose
  作者：Isidoro Izquierdo、Maria T. Plaza

  DOI：10.1080/07328309608005655

  日期：1996.4

  Reaction of 2,3:4,5-di-O-isopropylidene-beta-D-arabino-hexos-2-ulo-2,6-pyranose (1) with (methoxycarbonylmethylene)triphenylphosphorane in either dichloromethane or methanol gave methyl (E)-2,3-dideoxy-4,5:6,7-di-O-isopropylidene-beta-D-arabino-oct-2-ene-4-ulo-4,8-pyranosonate (2) or a 1:2.3 mixture of 2 and its Z-isomer (3), respectively. Bishydroxylation of 2 with osmium tetraoxide gave a mixture of methyl 4,5:6,7-di-O-isopropylidene-beta-D-glycero-D-galacto- (4) and -D-glycero-D-ido-oct-4-ulo-4,8-pyranosonate (5) which were carefully resolved by column chromatography. Compound 4 was transformed into its 2,3-di-O-methyl derivative (6) which was deacetonated to 7 and subsequently degraded to dimethyl 2,3-di-O-methyl-(+/-)-L-tartrate (8). On the other hand, acetonation of a mixture of 4 and 5 gave the corresponding tri-O-isopropylidene derivatives (9) and (10). Compounds 4 and 5 were reduced with LiAlH4 to the related 4,5:6,7-di-O-isopropylidene-beta-D-glycero-D-galacto- (11) and -beta-D-glycero-D-ido-oct-4-ulo-4,8-pyranose (12). Treatment of 11 and 12 with acetone/PTSA/CuSO4 only produced the acetonation at the C-2,3 positions. Finally, compounds 11 and 12 were deacetonated to the corresponding D-glycero-D-galacto- (15) and D-glycero-D-ido-oct-4-ulose (16).