Methyl (2S)-4-<(tert-butyldiphenylsilyl)oxy>-2-hydroxybutyrate | 153011-60-0

• 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 (2S)-4-<(tert-butyldiphenylsilyl)oxy>-2-hydroxybutyrate
• 英文别名: Methyl (2S)-4-[(tert-butyldiphenylsilyl)oxy]-2-hydroxybutyrate；(S)-Methyl 4-((tert-butyldiphenylsilyl)oxy)-2-hydroxybutanoate；methyl (2S)-4-[tert-butyl(diphenyl)silyl]oxy-2-hydroxybutanoate
• CAS: 153011-60-0
• 化学式: C₂₁H₂₈O₄Si
• 分子量: 372.536
• InChiKey: YKBMJQPUPULJBC-IBGZPJMESA-N

物化性质

• 沸点：
  447.5±45.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.49
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl (2S)-4-<(tert-butyldiphenylsilyl)oxy>-2-hydroxybutyrate 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 dimethyl sulfide borane 、 sodium methylate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.25h， 生成 (2S)-O-(tert-butyldiphenylsilyl)-1,2-epoxybutan-4-ol
  参考文献：
  名称：

  Total synthesis of (-)-tetrahydrolipstatin

  摘要：

  The total synthesis of (-)-tetrahydrolipstatin utilizing two approaches is described. In the first, L-malic acid was used as a chiral template to obtain enantiomerically pure (R)-3-(benzyloxy)-tetradecanal (11) which was chain-extended using 1-(trimethylsilyl)-2-nonene and a Lewis acid. This advanced intermediate was further elaborated to the target compound in good overall yield. The second approach utilized lauraldehyde as a starting material and capitalizes on an asymmetric allylboronation (91 % ee). The product could be obtained enantiomerically pure by conversion to the (R)-acetoxymandelate ester and hydrolysis. Oxidative cleavage of the terminal double bond led to 11 which was further extended using 1,3- and 1,2-asymmetric induction based on existing neighboring chirality. The synthesis of tetrahydrolipstatin using the second approach comprises seven steps from 11 and proceeds in 38 % overall yield.

  DOI：

  10.1021/jo00079a022
• 作为产物：
  描述：

  (S)-2-羟基琥珀酸甲酯 在 4-二甲氨基吡啶 、 dimethyl sulfide borane 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 Methyl (2S)-4-<(tert-butyldiphenylsilyl)oxy>-2-hydroxybutyrate
  参考文献：
  名称：

  The diastereoselective asymmetric total synthesis of NG-391, a neuronal cell-protecting molecule

  摘要：

  The stereocontrolled total synthesis of (+)-NG-391, a neuronal cell-protecting molecule, is described along with the determination of its absolute stereochemistry. The following reactions in this synthesis are particularly noteworthy: (1) The stereoselective construction of the conjugated (E,E,E,E,E)-pentaene from an (E,E,E)-alcohol using an IBX oxidation followed by stereoselective Horner-Emmons reaction. (2) The (E)-selective Knoevenagel condensation of a beta-ketonitrile with a chiral 2-alkoxyaldehyde prepared from (S)-malic acid. (3) A diastereoselective epoxidation. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)01290-5

文献信息

• Stereoselective Synthesis of the Glycosidase Inhibitor Australine through a One-Pot, Double-Cyclization Strategy
  作者：Celia Ribes、Eva Falomir、Miguel Carda、J. Alberto Marco

  DOI：10.1021/ol062570v

  日期：2007.1.1

  [reaction: see text] A stereocontrolled, convergent synthesis of the alkaloid australine, a glycosidase inhibitor of the pyrrolizidine class, is described. The chiral starting materials were ketone 3, derived from L-erythrulose, and alpha-alkoxy aldehyde 4, prepared from L-malic acid. A key step of the synthesis was the highly stereoselective aldol reaction between 4 and a Z boron enolate derived from

  [反应：见正文]描述了立体生物控制的，聚合的生物碱类奥特林的合成，吡咯烷嗪类的糖苷酶抑制剂。手性起始原料是衍生自L-赤藓糖的酮3和衍生自L-苹果酸的α-烷氧基醛4。合成的关键步骤是4与3衍生的Z硼烯醇盐之间的高立体选择性醛醇缩合反应。另一关键步骤是通过三步序列由SN2引起的SN2置换的一锅法构建双环吡咯嗪系统。偏苯三酸酯前体上的苄胺。
• Verfahren zur Herstellung von Oxetanonen
  申请人：F. HOFFMANN-LA ROCHE AG

  公开号：EP0189577A2

  公开（公告）日：1986-08-06

  Verfahren zur Herstellung von die Pankreaslipase hemmenden Oxetanonäthylester der Formel worin X Undecyl oder 2Z,5Z,Undecadienyl, C6 n-Hexyl, Y lsobutyl und Z Formyl, oder Y Carbamoylmethyl und Z Acetyl sind, durch Veresterung entsprechender Oxetanonäthanolen, durch Hydrierung der 3-Undecenylgruppe zur Undecyigruppe X in entsprechenden Ausgangsoxetanonäthylester oder durch N-Formylierung oder N--Acetylierung von entsprechenden primären Aminen.

  制备抑制胰脂肪酶的氧杂环庚烷乙酯的方法，其化学式中X为十一烷基或2Z,5Z,十一二烯基，C6 n-己基，Y为异丁基和Z为甲酰基，或Y为氨基甲基和Z为乙酰基，通过对应的氧杂环庚烷醇的酯化，通过在相应的起始氧杂环庚烷乙酯中氢化3-十一烯基到X的十一烷基，或通过对应的初级胺的N-甲酰化或N-乙酰化实现。
• Concise total syntheses of heliannuols B and D
  作者：Yuki Manabe、Makoto Kanematsu、Hiromasa Yokoe、Masahiro Yoshida、Kozo Shishido

  DOI：10.1016/j.tet.2013.11.070

  日期：2014.1

  Concise and efficient enantioselective total syntheses of heliannuols B and D have been accomplished using chirality transfer through a Lewis acid-promoted Claisen rearrangement for the construction of the C7 tertiary stereogenic center and a relay ring-closing metathesis for assembling the dihydrobenzo[b]oxepine backbone of the natural products as the key steps. (C) 2013 Elsevier Ltd. All rights reserved.
• J. Org. Chem. 1993, 58, 7768-7781
  作者：

  DOI：——

  日期：——
• Drug. Future 1994, 19, 1003
  作者：

  DOI：——

  日期：——