(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

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (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
• 英文别名: (2E,4S,5S,6E,8S,9R)-4-[tert-butyl(dimethyl)silyl]oxy-9-[(4R,5R)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]-8,9-bis(phenylmethoxy)nona-2,6-dien-5-ol
• 化学式: C₃₉H₅₈O₈Si
• 分子量: 682.97
• InChiKey: NJRHAQDAVNXRAP-OIPDPMJJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.71
• 重原子数：
  48
• 可旋转键数：
  16
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  84.8
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 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 、 草酰氯 、 (DHQ)2-PHAL 、 甲基磺酰胺 、 三氟化硼乙醚 、 四丁基碘化铵 、 sodium hydride 、 二异丁基氢化铝 、 potassium carbonate 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 三乙胺 、 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 37.75h， 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

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.