Methyl (2R,3S,4S,5R)-3,4,5-tris(benzyloxy)-2-(methoxymethoxy)-6-oxohexanoate | 158535-94-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl (2R,3S,4S,5R)-3,4,5-tris(benzyloxy)-2-(methoxymethoxy)-6-oxohexanoate
• 英文别名: methyl (2R,3S,4S,5R)-2-(methoxymethoxy)-6-oxo-3,4,5-tris(phenylmethoxy)hexanoate
• CAS: 158535-94-5
• 化学式: C₃₀H₃₄O₈
• 分子量: 522.595
• InChiKey: UTBXECKBXQLWHR-ICYKMPLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  38
• 可旋转键数：
  18
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Methyl (2R,3S,4S,5R)-3,4,5-tris(benzyloxy)-2-(methoxymethoxy)-6-oxohexanoate 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 1.5h， 以30%的产率得到dimethyl 2,3,4-tri-O-benzyl-β-L-idopyranosiduronate
  参考文献：
  名称：

  Synthesis of Protected Carbohydrate Derivatives Through Homologation of Threose and Erythrose Derivatives with Chiral .gamma.-Alkoxy Allylic Stannanes

  摘要：

  Additions of the gamma-alkoxy allylic stannanes (S)-1 and (R)-1 and the racemate (RS)-1 to the threose and erythrose aldehyde derivatives 6 and 15 in the presence of BF3.OEt(2) or MgBr2.OEt(2) were examined in order to establish stereochemical preferences. It was found that (S)-1 and aldehyde 6 afforded the syn,anti,syn adduct 7 in the BF3-promoted reaction, while (R)-1 and 6 gave the syn,syn,syn adduct 8 under MgBr2 conditions. Likewise, (S)-1 and aldehyde 15 yielded the syn,anti,anti adduct 16 with BF3, whereas (R)-1 and 15 led to the syn,syn,anti adduct 17 with MgBr2. The MgBr2-promoted reactions showed sufficient rate differences between the matched and mismatched stannanes to allow the use of racemic stannane (RS)-1 in just over 2-fold excess, whereupon the matched adducts 8 and 17 were favored by greater than 9:1 over the mismatched adducts. The major adducts 7, 8, 16, and 17 were converted to the hexose derivatives 21, 30/31, 34, and 39 by ozonolysis, selective deprotection, and refunctionalization. Adducts 16 and 17 were dihydroxylated with OsO4-NMO to the deoxyoctose precursors 40/41 and 42/43.

  DOI：

  10.1021/jo00091a034
• 作为产物：
  描述：

  Methyl (2R,3S,4R,5S)-3,4,5-tris(benzyloxy)-6-<(tert-butyldimethylsilyl)oxy>-2-(methoxymethoxy)hexanoate 在 四丁基氟化铵 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 20.33h， 生成 Methyl (2R,3S,4S,5R)-3,4,5-tris(benzyloxy)-2-(methoxymethoxy)-6-oxohexanoate
  参考文献：
  名称：

  Synthesis of Protected Carbohydrate Derivatives Through Homologation of Threose and Erythrose Derivatives with Chiral .gamma.-Alkoxy Allylic Stannanes

  摘要：

  Additions of the gamma-alkoxy allylic stannanes (S)-1 and (R)-1 and the racemate (RS)-1 to the threose and erythrose aldehyde derivatives 6 and 15 in the presence of BF3.OEt(2) or MgBr2.OEt(2) were examined in order to establish stereochemical preferences. It was found that (S)-1 and aldehyde 6 afforded the syn,anti,syn adduct 7 in the BF3-promoted reaction, while (R)-1 and 6 gave the syn,syn,syn adduct 8 under MgBr2 conditions. Likewise, (S)-1 and aldehyde 15 yielded the syn,anti,anti adduct 16 with BF3, whereas (R)-1 and 15 led to the syn,syn,anti adduct 17 with MgBr2. The MgBr2-promoted reactions showed sufficient rate differences between the matched and mismatched stannanes to allow the use of racemic stannane (RS)-1 in just over 2-fold excess, whereupon the matched adducts 8 and 17 were favored by greater than 9:1 over the mismatched adducts. The major adducts 7, 8, 16, and 17 were converted to the hexose derivatives 21, 30/31, 34, and 39 by ozonolysis, selective deprotection, and refunctionalization. Adducts 16 and 17 were dihydroxylated with OsO4-NMO to the deoxyoctose precursors 40/41 and 42/43.

  DOI：

  10.1021/jo00091a034

文献信息

• Synthesis of Protected Carbohydrate Derivatives Through Homologation of Threose and Erythrose Derivatives with Chiral .gamma.-Alkoxy Allylic Stannanes
  作者：James A. Marshall、Boris M. Seletsky、George P. Luke

  DOI：10.1021/jo00091a034

  日期：1994.6

  Additions of the gamma-alkoxy allylic stannanes (S)-1 and (R)-1 and the racemate (RS)-1 to the threose and erythrose aldehyde derivatives 6 and 15 in the presence of BF3.OEt(2) or MgBr2.OEt(2) were examined in order to establish stereochemical preferences. It was found that (S)-1 and aldehyde 6 afforded the syn,anti,syn adduct 7 in the BF3-promoted reaction, while (R)-1 and 6 gave the syn,syn,syn adduct 8 under MgBr2 conditions. Likewise, (S)-1 and aldehyde 15 yielded the syn,anti,anti adduct 16 with BF3, whereas (R)-1 and 15 led to the syn,syn,anti adduct 17 with MgBr2. The MgBr2-promoted reactions showed sufficient rate differences between the matched and mismatched stannanes to allow the use of racemic stannane (RS)-1 in just over 2-fold excess, whereupon the matched adducts 8 and 17 were favored by greater than 9:1 over the mismatched adducts. The major adducts 7, 8, 16, and 17 were converted to the hexose derivatives 21, 30/31, 34, and 39 by ozonolysis, selective deprotection, and refunctionalization. Adducts 16 and 17 were dihydroxylated with OsO4-NMO to the deoxyoctose precursors 40/41 and 42/43.