(2R)-2-[(2R,3S)-1-[tert-butyl(dimethyl)silyl]-3-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-4-oxoazetidin-2-yl]propanal | 158514-89-7

• 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: (2R)-2-[(2R,3S)-1-[tert-butyl(dimethyl)silyl]-3-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-4-oxoazetidin-2-yl]propanal
• CAS: 158514-89-7
• 化学式: C₂₀H₄₁NO₃Si₂
• 分子量: 399.721
• InChiKey: KYODVYXAEDTXOG-YLFCFFPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.06
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R)-2-[(2R,3S)-1-[tert-butyl(dimethyl)silyl]-3-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-4-oxoazetidin-2-yl]propanal 在 palladium diacetate potassium fluoride 、 sodium hydride 、 双(2-二苯基磷苯基)醚 作用下， 以 乙醇 、 甲苯 为溶剂， 反应 48.03h， 生成 ethyl (1S,5R,6S)-6-[(R)-1-tert-butyldimethylsilyloxyethyl]-1-methyl-carbapen-2-em-3-carboxylate
  参考文献：
  名称：

  钯催化的乙烯基卤化物酰胺化反应合成3-烷氧基羰基-1β-甲基卡巴南

  摘要：

  可以通过钯催化的C bondN键形成反应合成3-烷氧羰基-1β-甲基咔啉。在该反应中，使用Pd（OAc）2和DPEphos可获得良好的结果，并且在不存在碱的情况下生成Pd（0）对于提高产率是必需的。

  DOI：

  10.1016/s0040-4039(01)02091-3
• 作为产物：
  描述：

  (3S,4R)-3-[(R)-1-(tert-butyldimethylsilyloxy)ethyl-4-vinyl-2-azetidinone] 在 (2,5-norbornadiene)Rh⁺B^-Ph₄ 、 (S,S)bis(diphenylphosphino)pentane 、 氢气 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 70.0 ℃ 、8.27 MPa 条件下， 反应 42.0h， 生成 (2R)-2-[(2R,3S)-1-[tert-butyl(dimethyl)silyl]-3-[(1R)-1-[tert-butyl(dimethyl)silyl]oxyethyl]-4-oxoazetidin-2-yl]propanal
  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

文献信息

• Synthesis of 3-alkoxycarbonyl-1β-methylcarbapenem using palladium-catalyzed amidation of vinyl halide
  作者：Yuji Kozawa、Miwako Mori

  DOI：10.1016/s0040-4039(01)02091-3

  日期：2002.1

  3-Alkoxycarbonyl-1β-methylcarbapenem could be synthesized using a palladium-catalyzed CN bond-forming reaction. In this reaction, the use of Pd(OAc)2 and DPEphos gave a good result, and generation of Pd(0) in the absence of a base is necessary to increase the yield.

  可以通过钯催化的C bondN键形成反应合成3-烷氧羰基-1β-甲基咔啉。在该反应中，使用Pd（OAc）2和DPEphos可获得良好的结果，并且在不存在碱的情况下生成Pd（0）对于提高产率是必需的。
• A highly refined version of the α-keto ester based carbapenem synthesis: The total synthesis of meropenem
  作者：Amar S. Prashad、Nancy Vlahos、Paul Fabio、Gregg B. Feigelson

  DOI：10.1016/s0040-4039(98)01523-8

  日期：1998.9

  The α-keto ester based carbapenem synthesis has been refined so that all deprotections and the ring forming cyclization can be carried out in a single step.

  基于α-酮酯的碳青霉烯合成方法已经过完善，因此所有脱保护和成环环化反应都可以在一个步骤中完成。
• A new synthesis of 1β-methylcarbapenems using NBS-promoted cyclization as a key step
  作者：Osamu Sakurai、Masami Takahashi、Tsuyoshi Ogiku、Masahito Hayashi、Hiroshi Horikawa、Tameo Iwasaki

  DOI：10.1016/s0040-4039(00)73421-6

  日期：1994.8

  A novel construction of 1 beta-methylcarbapenem skeleton has been achieved by use of N-bromosuccinimide(NBS)-promoted cyclization as a key step. The mechanism of the stereospecific cyclization leading to 1 beta-methylcarbapenam is also discussed.
• Synthesis of 3-Alkoxycarbonyl-1β-methylcarbapenem by Using the Palladium-Catalyzed C−N Bond-Forming Reaction between Vinyl Halide and β-Lactam Nitrogen
  作者：Yuji Kozawa、Miwako Mori

  DOI：10.1021/jo020584i

  日期：2003.4.1

  3-Alkoxycarbonyl-1beta-methylcarbapenem could be synthesized by using a palladium-catalyzed C-N bond-forming reaction between vinyl halide and beta-lactam nitrogen. In this reaction, the use of Pd(OAc)(2) and DPEphos gave a good result, and the generation of Pd(0) from Pd(OAc)(2) in the absence of a base is necessary to increase the yield.
• Regio- and Stereoselective Synthesis of Key 1-Methyl Carbapenem Intermediates via Hydroformylation Using a Zwitterionic Rhodium Catalyst
  作者：H. S. Park、E. Alberico、H. Alper

  DOI：10.1021/ja993080j

  日期：1999.12.1

  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).