cis-1-(p-methoxyphenyl)-3-chloro-4-formyl-3-methyl-2-azetidinone

• 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: cis-1-(p-methoxyphenyl)-3-chloro-4-formyl-3-methyl-2-azetidinone
• 英文别名: (2R,3S)-3-chloro-1-(4-methoxyphenyl)-3-methyl-4-oxoazetidine-2-carbaldehyde
• 化学式: C₁₂H₁₂ClNO₃
• 分子量: 253.685
• InChiKey: GPBGOELWLHEXLB-PWSUYJOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  甲醇 、 cis-1-(p-methoxyphenyl)-3-chloro-4-formyl-3-methyl-2-azetidinone 在 sodium carbonate 作用下， 反应 3.0h， 以76%的产率得到5-Methoxy-4-(4-methoxy-phenylamino)-3-methyl-5H-furan-2-one
  参考文献：
  名称：

  碱基促进的顺式4-甲酰基-2-氮杂环丁烷酮的异构化：化学选择性C4表异构化与重排成环状烯胺酮。

  摘要：

  描述了两种简单，有效和互补的方法，用于顺式-4-甲酰基-2-氮杂环丁烷酮1-3的区域特异性C4表异构化。第一种方法是在苄基三丁基溴化铵（3-4 mol％）作为相转移催化剂的情况下，在室温下于苯的非均相介质中使用40％的二甲胺水溶液作为试剂。该转化耐受2-氮杂环丁酮环的C 3上的烷基，烯基，炔基，芳基和烷氧基取代基。然而，这种异构化的局限性如下：（i）仅可使用N-（对甲氧基苯基）-β-内酰胺，并且（ii）转化与键合于2-氮杂环丁酮C3位的杂原子取代基的相容性较低。环。对于这些问题的高度通用的解决方案取决于在不同溶剂中使用碳酸钠作为异构化试剂。

  DOI：

  10.1021/jo991984h
• 作为产物：
  描述：

  2-氯丙酰氯 、 1,4-bis(4'-methoxyphenyl)-1,4-diazabuta-1,3-diene 在 盐酸 、 三乙胺 作用下， 生成 、 cis-1-(p-methoxyphenyl)-3-chloro-4-formyl-3-methyl-2-azetidinone
  参考文献：
  名称：

  Stereoselective preparation of mono- and bis-.beta.-lactams by the 1,4-diaza-1,3-diene - acid chloride condensation: scope and synthetic applications

  摘要：

  The dehydrochlorination of a variety of acid chlorides with triethylamine in the presence of 1,4-diaza 1,3-dienes gives in fair to excellent yields, with total stereoselectivity, cis-4-imino beta-lactams 2, cis-4-formyl beta-lactams 3, or C4,C4'-bis-beta-lactams 4, depending on the reaction conditions. The reaction tolerates a wide variety of substituents, including alkoxy, thiophenoxy, amino, aryl, alkyl, alkylidene, and halogen groups, at the ketene moiety. The synthetic versatility of compounds 3 has been demonstrated by their conversion to intermediates in the synthesis of carbapenems PS-5 and PS-6. Base-induced isomerization of compounds 4 to novel bis-gamma-lactams 5, which in turn are aza analogs of glycaric acids, occurred with total retention of the configuration. This process is formally the elongation of glyoxal in four carbons bearing four contiguous stereocenters with total stereoselectivity in only three or four synthetic steps.

  DOI：

  10.1021/jo00048a027

文献信息

• Base-Promoted Isomerization of <i>cis</i>-4-Formyl-2-azetidinones:  Chemoselective <i>C</i>4-Epimerization vs Rearrangement to Cyclic Enaminones
  作者：Benito Alcaide、Moustafa F. Aly、Carolina Rodríguez、Alberto Rodríguez-Vicente

  DOI：10.1021/jo991984h

  日期：2000.6.1

  N-(p-methoxyphenyl)-beta-lactams can be used, and (ii) transformation is less compatible with heteroatomic substituents bonded to the C3 position of the 2-azetidinone ring. A highly general solution to these problems relies on the use of sodium carbonate as the isomerization reagent in different solvents. We also describe a novel base-promoted rearrangement of the beta-lactam ring to cyclic enaminones 6

  描述了两种简单，有效和互补的方法，用于顺式-4-甲酰基-2-氮杂环丁烷酮1-3的区域特异性C4表异构化。第一种方法是在苄基三丁基溴化铵（3-4 mol％）作为相转移催化剂的情况下，在室温下于苯的非均相介质中使用40％的二甲胺水溶液作为试剂。该转化耐受2-氮杂环丁酮环的C 3上的烷基，烯基，炔基，芳基和烷氧基取代基。然而，这种异构化的局限性如下：（i）仅可使用N-（对甲氧基苯基）-β-内酰胺，并且（ii）转化与键合于2-氮杂环丁酮C3位的杂原子取代基的相容性较低。环。对于这些问题的高度通用的解决方案取决于在不同溶剂中使用碳酸钠作为异构化试剂。
• Stereoselective preparation of mono- and bis-.beta.-lactams by the 1,4-diaza-1,3-diene - acid chloride condensation: scope and synthetic applications
  作者：Benito Alcaide、Yolanda Martin-Cantalejo、Javier Perez-Castells、Julian Rodriguez-Lopez、Miguel A. Sierra、Angeles Monge、Virginia Perez-Garcia

  DOI：10.1021/jo00048a027

  日期：1992.10

  The dehydrochlorination of a variety of acid chlorides with triethylamine in the presence of 1,4-diaza 1,3-dienes gives in fair to excellent yields, with total stereoselectivity, cis-4-imino beta-lactams 2, cis-4-formyl beta-lactams 3, or C4,C4'-bis-beta-lactams 4, depending on the reaction conditions. The reaction tolerates a wide variety of substituents, including alkoxy, thiophenoxy, amino, aryl, alkyl, alkylidene, and halogen groups, at the ketene moiety. The synthetic versatility of compounds 3 has been demonstrated by their conversion to intermediates in the synthesis of carbapenems PS-5 and PS-6. Base-induced isomerization of compounds 4 to novel bis-gamma-lactams 5, which in turn are aza analogs of glycaric acids, occurred with total retention of the configuration. This process is formally the elongation of glyoxal in four carbons bearing four contiguous stereocenters with total stereoselectivity in only three or four synthetic steps.