(3S,4S,5R)-5-hydroxy-4-<β-(trimethylsilyl)ethoxy>-3-vinyloxacyclohexan-2-one | 219726-52-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3S,4S,5R)-5-hydroxy-4-<β-(trimethylsilyl)ethoxy>-3-vinyloxacyclohexan-2-one
• 英文别名: (4R,5R,6R)-6-ethenyl-4-hydroxy-5-(2-trimethylsilylethoxy)oxan-2-one
• CAS: 219726-52-0
• 化学式: C₁₂H₂₂O₄Si
• 分子量: 258.39
• InChiKey: FYWIIZUGGJXRNY-CKYFFXLPSA-N

物化性质

• 沸点：
  361.214±42.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  1.042±0.10 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  (3S,4S,5R)-5-hydroxy-4-<β-(trimethylsilyl)ethoxy>-3-vinyloxacyclohexan-2-one 在 sodium hydroxide 、 四氧化锇 、 N-甲基吲哚酮 、 二甲基硫 、 三氟化硼乙醚 、 叔丁基锂 、 4-甲基苯磺酸吡啶 、 臭氧 、 溶剂黄146 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 叔丁醇 为溶剂， 反应 29.25h， 生成 3-deoxy-α-D-manno-oct-2-ulosonic acid
  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：

  (4R,5R,6R)-6-ethenyl-5-(2-trimethylsilylethoxy)oxane-2,4-diol 在 Celite 、 silver carbonate 作用下， 以 苯 为溶剂， 生成 (3S,4S,5R)-5-hydroxy-4-<β-(trimethylsilyl)ethoxy>-3-vinyloxacyclohexan-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

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.