(3S,4R)-3-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-1-methyl-4-vinyl-azetidin-2-one | 256371-24-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酰胺类
• 英文名称: (3S,4R)-3-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-1-methyl-4-vinyl-azetidin-2-one
• 英文别名: (3S,4R)-3-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-4-ethenyl-1-methylazetidin-2-one
• CAS: 256371-24-1
• 化学式: C₁₄H₂₇NO₂Si
• 分子量: 269.459
• InChiKey: KOWYCLKTSHHGKG-IJLUTSLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.04
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3S,4R)-3-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-1-methyl-4-vinyl-azetidin-2-one 在 (2,5-norbornadiene)Rh⁺B^-Ph₄ 、 (S,S)bis(diphenylphosphino)pentane 、 四丁基氟化铵 、 氢气 、 sodium hydride 作用下， 以 四氢呋喃 、 苯 为溶剂， -78.0~70.0 ℃ 、8.27 MPa 条件下， 反应 40.5h， 生成 3-[(2R,3S)-3-((R)-1-Methoxy-ethyl)-1-methyl-4-oxo-azetidin-2-yl]-propionaldehyde
  参考文献：
  名称：

  Regio- and Stereoselective Synthesis of Key 1-Methyl Carbapenem Intermediates via Hydroformylation Using a Zwitterionic Rhodium Catalyst

  摘要：

  The asymmetric hydroformylation of a 4-vinyl beta-lactam catalyzed by a rhodium catalyst with a chiral phosphine ligand was investigated. The catalytic system consisting of a zwitterionic rhodium catalyst, (NBD)Rh+(C6H5B-Ph3) 4, and (S,S)-2,4 bis(diphenylphosphino)pentane, (S,S)-BDPP, gave branched aldehydes in high regio- and stereoselectivity. The hydroformylated products are key intermediates in the synthesis of 1-methylcarbapenem antibiotics. Using (3S,4R)-3-[(R)-1-(tert-butyldimethyl-silyloxy)ethyl]-4-vinyl-2-azetidinone (5a) as the reactant afforded aldehydes in a 97:3 branched-to-linear ratio and 91:9 to beta- to alpha-branched isomers. The regio (branched/linear)- and stereoselectivity (beta/alpha) was >99:1 when (3S,4R)-1-N-BOC-3-[(R)-1-methoxyerhyl]-4-vinyl-2-azetidinone was used as the substrate (5q).

  DOI：

  10.1021/ja993080j
• 作为产物：
  描述：

  (3S,4R)-3-[(R)-1-(tert-butyldimethylsilyloxy)ethyl-4-vinyl-2-azetidinone] 、 碘甲烷 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 6.5h， 以95%的产率得到(3S,4R)-3-[(R)-1-(tert-Butyl-dimethyl-silanyloxy)-ethyl]-1-methyl-4-vinyl-azetidin-2-one
  参考文献：
  名称：

  Regio- and Stereoselective Synthesis of Key 1-Methyl Carbapenem Intermediates via Hydroformylation Using a Zwitterionic Rhodium Catalyst

  摘要：

  The asymmetric hydroformylation of a 4-vinyl beta-lactam catalyzed by a rhodium catalyst with a chiral phosphine ligand was investigated. The catalytic system consisting of a zwitterionic rhodium catalyst, (NBD)Rh+(C6H5B-Ph3) 4, and (S,S)-2,4 bis(diphenylphosphino)pentane, (S,S)-BDPP, gave branched aldehydes in high regio- and stereoselectivity. The hydroformylated products are key intermediates in the synthesis of 1-methylcarbapenem antibiotics. Using (3S,4R)-3-[(R)-1-(tert-butyldimethyl-silyloxy)ethyl]-4-vinyl-2-azetidinone (5a) as the reactant afforded aldehydes in a 97:3 branched-to-linear ratio and 91:9 to beta- to alpha-branched isomers. The regio (branched/linear)- and stereoselectivity (beta/alpha) was >99:1 when (3S,4R)-1-N-BOC-3-[(R)-1-methoxyerhyl]-4-vinyl-2-azetidinone was used as the substrate (5q).

  DOI：

  10.1021/ja993080j