methyl 4-<β-(trimethylsilyl)ethoxy>-2-butynoate | 219726-38-2

• 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 4-<β-(trimethylsilyl)ethoxy>-2-butynoate
• 英文别名: Methyl 4-(2-trimethylsilylethoxy)but-2-ynoate
• CAS: 219726-38-2
• 化学式: C₁₀H₁₈O₃Si
• 分子量: 214.337
• InChiKey: ICJLLIRDFLFQEV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.52
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 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 4-<β-(trimethylsilyl)ethoxy>-2-butynoate 在 吡啶 、 盐酸 、 6-溴-2-甲基苯酚 、 sodium cyanoborohydride 、 间氯过氧苯甲酸 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 叔丁醇 为溶剂， 反应 7.67h， 生成 (2R,3R)-2-[(E)-but-1-enyl]-3-(2-trimethylsilylethoxy)-2,3-dihydropyran-6-one
  参考文献：
  名称：

  Asymmetric Syn-Selective Aldol Reactions of γ-Oxygenated Vinylogous Urethane with a Second Generation Chiral Auxiliary:  Application in Construction of (+)-3-Deoxy-d-manno-2-octulosonic Acid

  摘要：

  Various examples of highly diastereoselective aldol reactions are presented where the nonracemic lithium enolate 6 derived from a C4-oxygenated vinylogous urethane reacts in syn fashion to provide upon intramolecular lactonization useful gamma-alkoxy-delta-lactone synthons 12a-f. In one particular example, the result of reaction with an acrolein surrogate, the lactone product 12e is applied in an efficient asymmetric synthesis of(+)-KDO (10 steps, 34% overall yield). Notable transformations include (1) hydrolysis of the vinylogous urethane functionality, (2) stereoselective reduction of the resulting beta-keto-lactone 2, (3) stereoselective dihydroxylation of the vinyl side chain of delta-lactone 17, and (4) addition of alpha-ethoxy-vinyllithium to the lactone carbonyl of 19 to procure the aldulosonic acid residue in 1 upon ozonolysis.

  DOI：

  10.1021/jo981916f
• 作为产物：
  描述：

  2-(三甲硅基)乙醇 在 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 methyl 4-<β-(trimethylsilyl)ethoxy>-2-butynoate
  参考文献：
  名称：

  Asymmetric total synthesis of (+)-phomalactone, (+)-acetylphomalactone and (+)-asperlin utilizing a novel syn-selective C4-oxa-vinylogous urethane

  摘要：

  The total synthesis of three natural products isolated from Nigrospora sp., Phoma sp., and Aspergillus nidulans(l) starting from an aldol reaction with a homochiral C-4-oxa-vinylogous urethane is described. Inherent stereoselectivity of the aldol reaction and overall alacrity of molecular construction are discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02675-6

文献信息

• Asymmetric <i>Syn</i>-Selective Aldol Reactions of γ-Oxygenated Vinylogous Urethane with a Second Generation Chiral Auxiliary:  Application in Construction of (+)-3-Deoxy-<scp>d</scp>-<i>manno</i>-2-octulosonic Acid
  作者：Richard H. Schlessinger、Liping H. Pettus

  DOI：10.1021/jo981916f

  日期：1998.11.1

  Various examples of highly diastereoselective aldol reactions are presented where the nonracemic lithium enolate 6 derived from a C4-oxygenated vinylogous urethane reacts in syn fashion to provide upon intramolecular lactonization useful gamma-alkoxy-delta-lactone synthons 12a-f. In one particular example, the result of reaction with an acrolein surrogate, the lactone product 12e is applied in an efficient asymmetric synthesis of(+)-KDO (10 steps, 34% overall yield). Notable transformations include (1) hydrolysis of the vinylogous urethane functionality, (2) stereoselective reduction of the resulting beta-keto-lactone 2, (3) stereoselective dihydroxylation of the vinyl side chain of delta-lactone 17, and (4) addition of alpha-ethoxy-vinyllithium to the lactone carbonyl of 19 to procure the aldulosonic acid residue in 1 upon ozonolysis.
• Asymmetric total synthesis of (+)-phomalactone, (+)-acetylphomalactone and (+)-asperlin utilizing a novel syn-selective C4-oxa-vinylogous urethane
  作者：Richard H. Schlessinger、Kevin W. Gillman

  DOI：10.1016/s0040-4039(98)02675-6

  日期：1999.2

  The total synthesis of three natural products isolated from Nigrospora sp., Phoma sp., and Aspergillus nidulans(l) starting from an aldol reaction with a homochiral C-4-oxa-vinylogous urethane is described. Inherent stereoselectivity of the aldol reaction and overall alacrity of molecular construction are discussed. (C) 1999 Elsevier Science Ltd. All rights reserved.