(2R,3S,4S,5R,6R,7S)-2,3,8-Tris<(tert-butyldimethylsilyl)oxy>-6,7-O-(1-methylethylidene)-5-hydroxyoctanoic acid γ-lactone | 151265-98-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3S,4S,5R,6R,7S)-2,3,8-Tris<(tert-butyldimethylsilyl)oxy>-6,7-O-(1-methylethylidene)-5-hydroxyoctanoic acid γ-lactone
• 英文别名: (3R,4S,5S)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[(R)-[(4S,5S)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-1,3-dioxolan-4-yl]-hydroxymethyl]oxolan-2-one
• CAS: 151265-98-4
• 化学式: C₂₉H₆₀O₈Si₃
• 分子量: 621.047
• InChiKey: NLUFQIBBILFOMW-KAGYXSEVSA-N

物化性质

• 沸点：
  585.6±50.0 °C(predicted)
• 密度：
  1.02±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  40
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.97
• 拓扑面积：
  92.7
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2R,3S,4S,5R,6R,7S)-2,3,8-Tris<(tert-butyldimethylsilyl)oxy>-6,7-O-(1-methylethylidene)-5-hydroxyoctanoic acid γ-lactone 在 对甲苯磺酸 作用下， 以88%的产率得到(2R,3S,4S,5R,6R,7S)-2,3,5,6,7,8-Hexahydroxyoctanoic acid γ-lactone
  参考文献：
  名称：

  Stereoselective synthesis of long-chain polyols by sequential homologation of enals with nonracemic .gamma.-silyloxy allylic stannanes and directed hydroxylation

  摘要：

  The nonracemic gamma-silyloxy allylic stannanes (S)-8 and (R)-8 add to the (R,R)-tartrate derived enals 7 and 24 to afford the adducts 9, 14, and 25. The bis-TBS derivatives 10, 15 and 22, upon hydroxylation with catalytic 0804-NMO, yield the differentially protected polyols 11, 16, and 23.

  DOI：

  10.1021/jo00074a004
• 作为产物：
  描述：

  6-<(tert-butyldimethylsilyl)oxy>-4(S),5(S)-(isopropylidenedioxy)-2(E)-hexen-1-ol 在 2,6-二甲基吡啶 、 四氧化锇 、 草酰氯 、 3 A molecular sieve 、 三氟化硼乙醚 、 二甲基亚砜 、 N-甲基吗啉氧化物 、 高碘酸 、 三乙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 23.75h， 生成 (2R,3S,4S,5R,6R,7S)-2,3,8-Tris<(tert-butyldimethylsilyl)oxy>-6,7-O-(1-methylethylidene)-5-hydroxyoctanoic 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

文献信息

• Stereoselective synthesis of long-chain polyols by sequential homologation of enals with nonracemic .gamma.-silyloxy allylic stannanes and directed hydroxylation
  作者：James A. Marshall、Serge Beaudoin、Krzysztof Lewinski

  DOI：10.1021/jo00074a004

  日期：1993.10

  The nonracemic gamma-silyloxy allylic stannanes (S)-8 and (R)-8 add to the (R,R)-tartrate derived enals 7 and 24 to afford the adducts 9, 14, and 25. The bis-TBS derivatives 10, 15 and 22, upon hydroxylation with catalytic 0804-NMO, yield the differentially protected polyols 11, 16, and 23.
• 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.