(2R,3S,4R,5S,6R)-Ethyl 4,5:6,7-bis-O-(1-methylethylidene)-2,3-dihydroxyheptanoate | 166945-70-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3S,4R,5S,6R)-Ethyl 4,5:6,7-bis-O-(1-methylethylidene)-2,3-dihydroxyheptanoate
• 英文别名: ethyl (2R,3R)-3-[(4R,5R)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]-2,3-dihydroxypropanoate
• CAS: 166945-70-6
• 化学式: C₁₅H₂₆O₈
• 分子量: 334.367
• InChiKey: IFQNITCNCNOZTH-LZQZFOIKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  104
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2R,3S,4R,5S,6R)-Ethyl 4,5:6,7-bis-O-(1-methylethylidene)-2,3-dihydroxyheptanoate 在 四丁基碘化铵 、 sodium hydride 、 1-羟基苯并三唑 、 O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate 、 溶剂黄146 、 sodium sulfate 、 三乙胺 、 lithium hydroxide 作用下， 以 四氢呋喃 、 乙醇 、 氯仿 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 42.0h， 生成 (3aS,4S,5R,14bS,14cR)-4,5-bis(benzyloxy)-12-methoxy-2,2-dimethyl-3a,4,5,8,9,14,14 b,14c-octahydro-6H-[1,3]dioxolo[4’’,5’’:3’,4’]azepino[1’,2’:1,2]pyrido[3,4-b]indol-6-one
  参考文献：
  名称：

  12,13-二苄基-banistenoside B 及其类似物的全合成

  摘要：

  报道了 Banistenoside B 的二苄基衍生物的全合成。关键步骤涉及使用 Pictet-Spengler 反应和分子内酰胺偶联构建 6.5.6.7 四环核心。X射线晶体学证实了重要化合物的立体化学。

  DOI：

  10.1002/ejoc.202200222
• 作为产物：
  描述：

  1,2:3,4-di-O-isopropylidene-D-mannitol 在 sodium periodate 、 四氧化锇 、 (DHQ)2-PHAL 、 甲基磺酰胺 、 sodium hydride 、 potassium carbonate 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 水 、 叔丁醇 为溶剂， 反应 27.25h， 生成 (2R,3S,4R,5S,6R)-Ethyl 4,5:6,7-bis-O-(1-methylethylidene)-2,3-dihydroxyheptanoate
  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.
• Total Synthesis of 12,13‐Dibenzyl‐banistenoside B and Analogs
  作者：Suhag S. Patil、Gorakhnath R. Jachak、Gamidi Rama Krishna、Narshinha P. Argade、D. Srinivasa Reddy

  DOI：10.1002/ejoc.202200222

  日期：2022.5.19

  The total synthesis of a dibenzyl derivative of Banistenoside B is reported. The key steps involve construction of 6.5.6.7 tetracyclic core using Pictet−Spengler reaction and intramolecular amide coupling. The stereochemistry of important compounds was confirmed by X-ray crystallography.

  报道了 Banistenoside B 的二苄基衍生物的全合成。关键步骤涉及使用 Pictet-Spengler 反应和分子内酰胺偶联构建 6.5.6.7 四环核心。X射线晶体学证实了重要化合物的立体化学。