ethyl (6E,2S,3S,5R,9R)-9-(tert-butyldimethylsiloxy)-3-hydroxy-2,4,4,6-tetramethyl-5-(trimethylsiloxy)tetradec-6-enoate | 220484-21-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: ethyl (6E,2S,3S,5R,9R)-9-(tert-butyldimethylsiloxy)-3-hydroxy-2,4,4,6-tetramethyl-5-(trimethylsiloxy)tetradec-6-enoate
• 英文别名: ethyl (E,2S,3S,5R,9R)-9-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-2,4,4,6-tetramethyl-5-trimethylsilyloxytetradec-6-enoate
• CAS: 220484-21-9
• 化学式: C₂₉H₆₀O₅Si₂
• 分子量: 544.963
• InChiKey: HFJRXITZDZUZSY-FJBYWKJNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  36
• 可旋转键数：
  18
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl (6E,2S,3S,5R,9R)-9-(tert-butyldimethylsiloxy)-3-hydroxy-2,4,4,6-tetramethyl-5-(trimethylsiloxy)tetradec-6-enoate 在 camphor-10-sulfonic acid 、 柠檬酸 作用下， 以 甲醇 、 丙酮 为溶剂， 反应 0.25h， 生成 ethyl (6E,2S,3S,5R,9R)-9-(tert-butyldimethylsiloxy)-3,5-dihydroxy-3,5-O-isopropylidene-2,4,4,6-tetramethyltetradec-6-enoate
  参考文献：
  名称：

  A Study Directed to the Asymmetric Synthesis of the Antineoplastic Macrolide Acutiphycin under Enantioselective Acyclic Stereoselection Based on Chiral Oxazaborolidinone-Promoted Asymmetic Aldol Reactions

  摘要：

  A shortening of the reaction path can be realized by using a series of the chiral oxazaborolidinone-promoted aldol reaction with respect to the practical synthesis of the (+)-acutiphycin seco acid derivative 5. The linear strategy is based on the utilization of five aldol reactions with a sequence of silyl nucleophiles, 7, 8, 35, 10, and 11, in the presence of stoichiometric amounts of the promoter, 1 or 2. The construction of the relative configuration between the stereogenic centers is diastereoselectively controlled by the stereochemistry of the promoter used in the enantioselective aldol reaction, which is nearly independent of that of the substrate (promoter control).

  DOI：

  10.1021/jo990342r
• 作为产物：
  描述：

  ethyl (-)-(3R)-3-hydroxyoctanoate 在 咪唑 、 2,6-二甲基吡啶 、 草酰氯 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 、 (S)-4-Isopropyl-3-tosyl-[1,3,2]oxazaborolidin-5-one 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 苯 为溶剂， 反应 47.33h， 生成 ethyl (6E,2S,3S,5R,9R)-9-(tert-butyldimethylsiloxy)-3-hydroxy-2,4,4,6-tetramethyl-5-(trimethylsiloxy)tetradec-6-enoate
  参考文献：
  名称：

  A Study Directed to the Asymmetric Synthesis of the Antineoplastic Macrolide Acutiphycin under Enantioselective Acyclic Stereoselection Based on Chiral Oxazaborolidinone-Promoted Asymmetic Aldol Reactions

  摘要：

  A shortening of the reaction path can be realized by using a series of the chiral oxazaborolidinone-promoted aldol reaction with respect to the practical synthesis of the (+)-acutiphycin seco acid derivative 5. The linear strategy is based on the utilization of five aldol reactions with a sequence of silyl nucleophiles, 7, 8, 35, 10, and 11, in the presence of stoichiometric amounts of the promoter, 1 or 2. The construction of the relative configuration between the stereogenic centers is diastereoselectively controlled by the stereochemistry of the promoter used in the enantioselective aldol reaction, which is nearly independent of that of the substrate (promoter control).

  DOI：

  10.1021/jo990342r

文献信息

• Toward a practical synthesis of acutiphycin. Highly stereoselective synthesis of C10-epi seco acid derivative via reaction paths shortened by using a series of chiral oxazaborolidinone-promoted aldol reactions
  作者：Mostofa Abu Hena、Chul-Sa Kim、Michio Horiike、Syun-ichi Kiyooka

  DOI：10.1016/s0040-4039(98)02553-2

  日期：1999.2
• Novel diastereo- and enantioselectivities in the chiral oxazaborolidinone-promoted asymmetric aldol reaction of highly hindered aldehydes having a quaternary carbon at α position and limitations observed on catalyst (promoter) control
  作者：Syun-ichi Kiyooka、Hirofumi Maeda、Mostofa Abu Hena、Mai Uchida、Chul-Sa Kim、Michio Horiike

  DOI：10.1016/s0040-4039(98)01808-5

  日期：1998.11

  The chiral oxazaborolidinone (1 and 2) -promoted asymmetric aldol reaction of pivalaldehyde with silyl nucleophile 3 resulted in excellent syn selectivity of the corresponding aldol with 96% ee. The catalyst (promoter) control was examined in the reaction with highly hindered aldehydes, 4 and 9. The reaction of 4 in the presence of 2 gave almost enantiopure aldol 7 (>50 : 1) with syn selectivity (4 : 1) in good yield. (C) 1998 Elsevier Science Ltd. All rights reserved.
• A Study Directed to the Asymmetric Synthesis of the Antineoplastic Macrolide Acutiphycin under Enantioselective Acyclic Stereoselection Based on Chiral Oxazaborolidinone-Promoted Asymmetic Aldol Reactions
  作者：Syun-ichi Kiyooka、Mostofa A. Hena

  DOI：10.1021/jo990342r

  日期：1999.7.1

  A shortening of the reaction path can be realized by using a series of the chiral oxazaborolidinone-promoted aldol reaction with respect to the practical synthesis of the (+)-acutiphycin seco acid derivative 5. The linear strategy is based on the utilization of five aldol reactions with a sequence of silyl nucleophiles, 7, 8, 35, 10, and 11, in the presence of stoichiometric amounts of the promoter, 1 or 2. The construction of the relative configuration between the stereogenic centers is diastereoselectively controlled by the stereochemistry of the promoter used in the enantioselective aldol reaction, which is nearly independent of that of the substrate (promoter control).