Acrylic acid (S)-1-{(2S,4R,6S)-4-acetoxy-6-[2-(tert-butyl-diphenyl-silanyloxy)-ethyl]-tetrahydro-pyran-2-ylmethyl}-but-3-enyl ester | 288092-47-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Acrylic acid (S)-1-{(2S,4R,6S)-4-acetoxy-6-[2-(tert-butyl-diphenyl-silanyloxy)-ethyl]-tetrahydro-pyran-2-ylmethyl}-but-3-enyl ester
• 英文别名: [(2S)-1-[(2S,4R,6S)-4-acetyloxy-6-[2-[tert-butyl(diphenyl)silyl]oxyethyl]oxan-2-yl]pent-4-en-2-yl] prop-2-enoate
• CAS: 288092-47-7
• 化学式: C₃₃H₄₄O₆Si
• 分子量: 564.794
• InChiKey: LNYSIZHGGSPAKS-FKWFRFQNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  40
• 可旋转键数：
  16
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Acrylic acid (S)-1-{(2S,4R,6S)-4-acetoxy-6-[2-(tert-butyl-diphenyl-silanyloxy)-ethyl]-tetrahydro-pyran-2-ylmethyl}-but-3-enyl ester 在 Grubbs catalyst first generation titanium(IV) isopropylate 作用下， 以 二氯甲烷 为溶剂， 反应 21.0h， 以73%的产率得到Acetic acid (2S,4R,6S)-2-[2-(tert-butyl-diphenyl-silanyloxy)-ethyl]-6-((S)-6-oxo-3,6-dihydro-2H-pyran-2-ylmethyl)-tetrahydro-pyran-4-yl ester
  参考文献：
  名称：

  Synthetic studies directed toward the phorboxazoles: preparation of the C3–C15 bisoxane segment and two stereoisomers

  摘要：

  A synthetic approach to the C3-C15 segment of the cytotoxic marine metabolite phorboxazoles is described. This segment consists of a methylene linked bisoxane structure. The first pyran ring was constructed by a Lewis acid catalyzed diene-aldehyde cyclo-condensation. The beta-C-glucoside substitution pattern of this ring was established by a stereoselective allylation. Ozonolysis of vinyl group and enantioselective allylation of the racemic aldehyde generated two separable homoallylic alcohols (-)-22 and (+)-23. The Mosher's esters of each alcohol were determined to be >90% de. Reaction of (-)-22 with acryloyl chloride, followed by ring closing metathesis gave the dihydro-2-pyrone target (-)-5. Mitsunobu inversion of (+)-23 with p-nitrobenzoic acid, hydrolysis, and esterification with acryloyl chloride and ring closing metathesis gave pseudoenantiomeric segment (+)-6. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(02)00613-0
• 作为产物：
  描述：

  (2R,6R)-2-[2-(tert-Butyl-diphenyl-silanyloxy)-ethyl]-6-methoxy-tetrahydro-pyran-4-one 在 4-二甲氨基吡啶 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 sodium acetate 、 L-Selectride 、 臭氧 、 三乙胺 、 (-)-B-methoxydiisopinocampheylborane 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 15.88h， 生成 Acrylic acid (S)-1-{(2S,4R,6S)-4-acetoxy-6-[2-(tert-butyl-diphenyl-silanyloxy)-ethyl]-tetrahydro-pyran-2-ylmethyl}-but-3-enyl ester
  参考文献：
  名称：

  Synthetic studies directed toward the phorboxazoles: preparation of the C3–C15 bisoxane segment and two stereoisomers

  摘要：

  A synthetic approach to the C3-C15 segment of the cytotoxic marine metabolite phorboxazoles is described. This segment consists of a methylene linked bisoxane structure. The first pyran ring was constructed by a Lewis acid catalyzed diene-aldehyde cyclo-condensation. The beta-C-glucoside substitution pattern of this ring was established by a stereoselective allylation. Ozonolysis of vinyl group and enantioselective allylation of the racemic aldehyde generated two separable homoallylic alcohols (-)-22 and (+)-23. The Mosher's esters of each alcohol were determined to be >90% de. Reaction of (-)-22 with acryloyl chloride, followed by ring closing metathesis gave the dihydro-2-pyrone target (-)-5. Mitsunobu inversion of (+)-23 with p-nitrobenzoic acid, hydrolysis, and esterification with acryloyl chloride and ring closing metathesis gave pseudoenantiomeric segment (+)-6. (C) 2002 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(02)00613-0

文献信息

• Phorboxazole synthetic studies: the C3–C15 bis-oxane segment
  作者：Patrick B Greer、William A Donaldson

  DOI：10.1016/s0040-4039(00)00530-x

  日期：2000.5

  The enantioselective synthesis of the C3-C15 bis-oxane segment of the phorboxazoles has been accomplished from 3-t-butyldiphenylsilyloxypropanal in 9 steps (>90% ee). (C) 2000 Elsevier Science Ltd. Ail rights reserved.