(4S,5R,6R,7R,8R)-2,3-Bis(benzyloxy)-4,5:6,7-bis-O-(1-methylethylidene)-2-nonen-1-ol | 166945-75-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (4S,5R,6R,7R,8R)-2,3-Bis(benzyloxy)-4,5:6,7-bis-O-(1-methylethylidene)-2-nonen-1-ol
• 英文别名: (E,4S,5R)-5-[(4R,5R)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]-4,5-bis(phenylmethoxy)pent-2-en-1-ol
• CAS: 166945-75-1
• 化学式: C₂₉H₃₈O₇
• 分子量: 498.617
• InChiKey: YXOPNOIAEFBVPL-KNIBJTMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  36
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  75.6
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (4S,5R,6R,7R,8R)-2,3-Bis(benzyloxy)-4,5:6,7-bis-O-(1-methylethylidene)-2-nonen-1-ol 在 草酰氯 、 三氟化硼乙醚 、 二甲基亚砜 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.75h， 生成 (4S,5S,8S,9R,10R,11R,12R)-8,9-Bis(benzyloxy)-4-<(tert-butyldimethylsilyl)oxy>-10,11:12,13-bis-O-(1-methylethylidene)-2,6-tridecadien-5-ol
  参考文献：
  名称：

  Stereoselective Synthesis of Higher Sugars by Homologation of Carbohydrate-Derived Enals with Nonracemic .gamma.-(Silyloxy) Allylic Stannanes and Substrate-Directed Hydroxylation

  摘要：

  A strategy is described for the chain extension of carbohydrate derivatives utilizing sequential Horner-Emmons condensation and then reduction-oxidation to prepare the enal homologue VII, which is converted to the corresponding dienyl bis-OTBS derivative IX upon condensation with a gamma-(silyloxy) allylic stannane VI and subsequent silylation. Dihydroxylation of dienes M with OsO4-NMO leads to syn,anti,syn,anti,syn. hexol derivatives X with excellent diastereoselectivity. These hexols undergo selective oxidative cleavage with H5IO6 to yield gamma-lactols XI. The methodology has been used to prepare the octonic lactone 15 from (S,S)-dimethyl tartrate and the undeconic lactone 32 from D-mannitol.

  DOI：

  10.1021/jo00101a020
• 作为产物：
  描述：

  1,2:3,4-di-O-isopropylidene-D-mannitol 在 sodium periodate 、 四氧化锇 、 二苯并-18-冠醚-6 、 (DHQ)2-PHAL 、 甲基磺酰胺 、 四丁基碘化铵 、 sodium hydride 、 二异丁基氢化铝 、 potassium carbonate 、 戴斯-马丁氧化剂 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 36.0h， 生成 (4S,5R,6R,7R,8R)-2,3-Bis(benzyloxy)-4,5:6,7-bis-O-(1-methylethylidene)-2-nonen-1-ol
  参考文献：
  名称：

  Stereoselective Synthesis of Higher Sugars by Homologation of Carbohydrate-Derived Enals with Nonracemic .gamma.-(Silyloxy) Allylic Stannanes and Substrate-Directed Hydroxylation

  摘要：

  A strategy is described for the chain extension of carbohydrate derivatives utilizing sequential Horner-Emmons condensation and then reduction-oxidation to prepare the enal homologue VII, which is converted to the corresponding dienyl bis-OTBS derivative IX upon condensation with a gamma-(silyloxy) allylic stannane VI and subsequent silylation. Dihydroxylation of dienes M with OsO4-NMO leads to syn,anti,syn,anti,syn. hexol derivatives X with excellent diastereoselectivity. These hexols undergo selective oxidative cleavage with H5IO6 to yield gamma-lactols XI. The methodology has been used to prepare the octonic lactone 15 from (S,S)-dimethyl tartrate and the undeconic lactone 32 from D-mannitol.

  DOI：

  10.1021/jo00101a020

文献信息

• Stereoselective Synthesis of Higher Sugars by Homologation of Carbohydrate-Derived Enals with Nonracemic .gamma.-(Silyloxy) Allylic Stannanes and Substrate-Directed Hydroxylation
  作者：James A. Marshall、Serge Beaudoin

  DOI：10.1021/jo00101a020

  日期：1994.11

  A strategy is described for the chain extension of carbohydrate derivatives utilizing sequential Horner-Emmons condensation and then reduction-oxidation to prepare the enal homologue VII, which is converted to the corresponding dienyl bis-OTBS derivative IX upon condensation with a gamma-(silyloxy) allylic stannane VI and subsequent silylation. Dihydroxylation of dienes M with OsO4-NMO leads to syn,anti,syn,anti,syn. hexol derivatives X with excellent diastereoselectivity. These hexols undergo selective oxidative cleavage with H5IO6 to yield gamma-lactols XI. The methodology has been used to prepare the octonic lactone 15 from (S,S)-dimethyl tartrate and the undeconic lactone 32 from D-mannitol.