(2R,3S,4S,5R,6R,7R,8R,9S,10S,11R,12R)-8,9-Bis(benzyloxy)-4,5-bis<(tert-butyldimethylsilyl)oxy>-10,11:12,13-bis-O-(1-methylethylidene)-2,3,5,6-tridecanetetrol | 166945-67-1

• 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: (2R,3S,4S,5R,6R,7R,8R,9S,10S,11R,12R)-8,9-Bis(benzyloxy)-4,5-bis<(tert-butyldimethylsilyl)oxy>-10,11:12,13-bis-O-(1-methylethylidene)-2,3,5,6-tridecanetetrol
• 英文别名: (2R,3S,4S,5S,6S,7S,8S,9R)-4,5-bis[[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)nonane-2,3,6,7-tetrol
• CAS: 166945-67-1
• 化学式: C₄₅H₇₆O₁₂Si₂
• 分子量: 865.262
• InChiKey: FYCWJEBNGSLIST-OYVQWYLHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.07
• 重原子数：
  59
• 可旋转键数：
  21
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  155
• 氢给体数：
  4
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  (2R,3S,4S,5R,6R,7R,8R,9S,10S,11R,12R)-8,9-Bis(benzyloxy)-4,5-bis<(tert-butyldimethylsilyl)oxy>-10,11:12,13-bis-O-(1-methylethylidene)-2,3,5,6-tridecanetetrol 在 3 A molecular sieve 、 高碘酸 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 5.0h， 生成 (2R,3S,4R,5R,6R,7S,8S,9R,10R)-6,7-Bis(benzyloxy)-2,3-bis<(tert-butyldimethylsilyl)oxy>-8,9:10,11-bis-O-(1-methylethylidene)-5-hydroxyundecanoic acid γ-lactone
  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：

  (4S,8S,9R,10R,11R,12R)-8,9-Bis(benzyloxy)-4,5-bis<(tert-butyldimethylsilyl)oxy>-10,11:12,13-bis-O-(1-methylethylidene)-2,6-tridecadiene 在 四氧化锇 、 N-甲基吗啉氧化物 作用下， 以 丙酮 为溶剂， 反应 16.0h， 以87%的产率得到(2R,3S,4S,5R,6R,7R,8R,9S,10S,11R,12R)-8,9-Bis(benzyloxy)-4,5-bis<(tert-butyldimethylsilyl)oxy>-10,11:12,13-bis-O-(1-methylethylidene)-2,3,5,6-tridecanetetrol
  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.