methyl (E,4S,5S)-5-[tert-butyl(dimethyl)silyl]oxy-4,6-dimethylhept-2-enoate | 676548-75-7

• 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: methyl (E,4S,5S)-5-[tert-butyl(dimethyl)silyl]oxy-4,6-dimethylhept-2-enoate
• CAS: 676548-75-7
• 化学式: C₁₆H₃₂O₃Si
• 分子量: 300.514
• InChiKey: YBIPUHUWFWNNGC-GGBPEREOSA-N

物化性质

• 沸点：
  325.5±25.0 °C(Predicted)
• 密度：
  0.902±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (E,4S,5S)-5-[tert-butyl(dimethyl)silyl]oxy-4,6-dimethylhept-2-enoate 在 二异丁基氢化铝 、 戴斯-马丁氧化剂 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 (E,3S,5S,7R,10S,11S)-1,11-bis[[tert-butyl(dimethyl)silyl]oxy]-3-[(4-methoxyphenyl)methoxy]-10,12-dimethyltridec-8-ene-5,7-diol
  参考文献：
  名称：

  Remote 1,5-stereoinduction in boron aldol reactions of methyl ketones: application to the convergent assembly of the 1,3-polyol sequence of (+)-roxaticin

  摘要：

  By exploiting 1,5-anti stereoinduction in the boron aldol coupling of the beta -alkoxy methyl ketones 6 and 8 with aldehydes 7 and 9, the convergent synthesis of 2, corresponding to the fully protected polyol sequence of the 30-membered macrolide, (+)-roxaticin (1), was achieved in an efficient manner (15 steps and 24.0% yield from ketone 15). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)02205-x
• 作为产物：
  描述：

  (2S,4R,5S)-2-Benzyloxy-5-(tert-butyl-dimethyl-silanyloxy)-4,6-dimethyl-heptan-3-one 在 palladium dihydroxide sodium periodate 、 lithium aluminium tetrahydride 、 氢气 作用下， 以 甲醇 、 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 24.67h， 生成 methyl (E,4S,5S)-5-[tert-butyl(dimethyl)silyl]oxy-4,6-dimethylhept-2-enoate
  参考文献：
  名称：

  Remote 1,5-stereoinduction in boron aldol reactions of methyl ketones: application to the convergent assembly of the 1,3-polyol sequence of (+)-roxaticin

  摘要：

  By exploiting 1,5-anti stereoinduction in the boron aldol coupling of the beta -alkoxy methyl ketones 6 and 8 with aldehydes 7 and 9, the convergent synthesis of 2, corresponding to the fully protected polyol sequence of the 30-membered macrolide, (+)-roxaticin (1), was achieved in an efficient manner (15 steps and 24.0% yield from ketone 15). (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)02205-x

文献信息

• Total Synthesis of the Polyene-Polyol Macrolide RK-397, Featuring Cross-Couplings of Alkynylepoxide Modules
  作者：Svetlana A. Burova、Frank E. McDonald

  DOI：10.1021/ja039618+

  日期：2004.3.3

  from alkyne-epoxide couplings are converted into 1,3-diols by a sequence of hydroxyl-directed hydrosilylation, C-Si bond oxidation, and stereoselective ketone reduction with induction from the beta-hydroxyl group. The highly convergent nature of our synthetic pathway and the flexibility of the modular synthesis strategy for virtually any stereoisomer can provide access to other members of the polyene-polyol

  天然产物 RK-397 的全合成基于组装聚乙酸酯结构的新合成策略，通过亲核末端炔烃模块与在相反末端带有另一个炔烃的亲电环氧化物的有效交叉偶联。天然产物由四个主要模块构成：碳 3-9 的多烯前体和碳 10-16、17-22 和 23-33 的三个炔烃封端模块。每个模块都是在控制所有立体化学元素的情况下制备的，从炔烃-环氧化物偶联获得的炔醇通过一系列羟基导向的氢化硅烷化、C-Si 键氧化和立体选择性酮还原反应转化为 1,3-二醇来自β-羟基。
• Diastereoselective synthesis of protected syn 1,3-diols by base-catalyzed intramolecular conjugate addition of hemiacetal-derived alkoxide nucleophiles
  作者：David A. Evans、Joelle A. Gauchet-Prunet

  DOI：10.1021/jo00061a018

  日期：1993.4

  Reaction of the illustrated unsaturated hydroxy esters (X = OMe, R2 = H, Me) and amides (X = N(Me)OMe, R2 = H, Me) with benzaldehyde and potassium alkoxide or amide bases is reported. The resulting benzylidene acetals are obtained in good yields (71-84%) and with high selectivity (>90: 10). In addition to an exploration of the scope of the reaction, a mechanistic study, involving the use of deuterated benzaldehyde to ascertain the rate-determining step of the process, is described.
• Evans David A., Gauchet-Prunet Joelle A., J. Org. Chem., 58 (1993) N 9, S 2446-2453
  作者：Evans David A., Gauchet-Prunet Joelle A.

  DOI：——

  日期：——