methyl (E)-3-[(2S)-2-(3-methoxypentan-3-yl)pyrrolidin-1-yl]-4-(2-trimethylsilylethoxy)but-2-enoate | 219726-36-0

• 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 (E)-3-[(2S)-2-(3-methoxypentan-3-yl)pyrrolidin-1-yl]-4-(2-trimethylsilylethoxy)but-2-enoate
• CAS: 219726-36-0
• 化学式: C₂₀H₃₉NO₄Si
• 分子量: 385.619
• InChiKey: OZRRCQARWIBNIO-ODECOBMASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.07
• 重原子数：
  26
• 可旋转键数：
  12
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  48
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl (E)-3-[(2S)-2-(3-methoxypentan-3-yl)pyrrolidin-1-yl]-4-(2-trimethylsilylethoxy)but-2-enoate 在 盐酸 、 6-溴-2-甲基苯酚 、 sodium cyanoborohydride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 5.67h， 生成 (5R,6R)-4-[(2S)-2-(3-methoxypentan-3-yl)pyrrolidin-1-yl]-6-phenyl-5-(2-trimethylsilylethoxy)oxan-2-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：

  7,7-dimethyl-4-oxa-7-sila-1-octyne 在 正丁基锂 作用下， 以 叔丁醇 为溶剂， 反应 4.25h， 生成 methyl (E)-3-[(2S)-2-(3-methoxypentan-3-yl)pyrrolidin-1-yl]-4-(2-trimethylsilylethoxy)but-2-enoate
  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

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.