cis-1-(p-methoxyphenyl)-4-formyl-3-phenyl-2-azetidinone | 133505-02-9

• 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)-4-formyl-3-phenyl-2-azetidinone
• 英文别名: (2S,3S)-1-(4-methoxyphenyl)-4-oxo-3-phenylazetidine-2-carbaldehyde
• CAS: 133505-02-9
• 化学式: C₁₇H₁₅NO₃
• 分子量: 281.311
• InChiKey: UUWPAMKJNUYXKP-CVEARBPZSA-N

物化性质

• 沸点：
  543.0±50.0 °C(Predicted)
• 密度：
  1.293±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 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：

  cis-1-(p-methoxyphenyl)-4-formyl-3-phenyl-2-azetidinone 在 sodium tetrahydroborate 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 19.0h， 生成 3-hydroxy-N-(4-methoxyphenyl)-2-phenylpropanamide
  参考文献：
  名称：

  Stereoselective Synthesis of 3-Substituted 4-(Formyloxy)-2-azetidinones by the Unusual Baeyer−Villiger Reaction of β-Lactam Aldehydes. Scope and Synthetic Applications

  摘要：

  The Baeyer-Villiger oxidation of 4-formyl-beta-lactams 1 with m-CPBA gave 4-(formyloxy) beta-lactams 2 in a simple, efficient, and totally stereoselective process. This reaction is one of the scarce examples of the preferred migration of a carbon moiety in an aliphatic aldehyde. The influence of the substituents at N1 and C3 of the four-membered ring in the Baeyer-Villiger rearrangement has been studied. Thus, alkyl, alkenyl, aryl, and alkyloxy 3-substituted-1-(p-anisyl)-2-azetidinone 1 form exclusively 4-(formyloxy) beta-lactams 2. Amide or acetoxy substituents at C3 of the four-membered ring produce mixtures of 4-(formyloxy) beta-lactams 2 and 4-carboxy beta-lactams 5. The exclusive formation of carboxy derivatives is observed sometimes for 1-alkyl-substituted-2-azetidinones 1. 4-(Formyloxy) beta-lactams 2 are suitable starting materials to prepare different 4-unsubstituted beta-lactams 9 using beta-hydroxy amides 8 as isolable intermediates. The overall transformation 4-formyl-2-azetidinone to 4-unsubstituted beta-lactam is an easy and convenient stereoselective route to these interesting types of compounds.

  DOI：

  10.1021/jo9612685
• 作为产物：
  描述：

  1,4-bis(4'-methoxyphenyl)-1,4-diazabuta-1,3-diene 在 盐酸 、 三乙胺 作用下， 以 甲苯 为溶剂， 反应 1.5h， 生成 cis-1-(p-methoxyphenyl)-4-formyl-3-phenyl-2-azetidinone
  参考文献：
  名称：

  A novel, general, totally stereoselective one-pot synthesis of cis-3-substituted 4-formylazetidin-2-ones

  摘要：

  A general, totally stereoselective one-pot synthesis of cis-3-substituted-4-formylazetidin-2-ones based upon the reaction of acid chlorides and 1,4-bis-(4-methoxyphenyl)-1,4-diazabuta-1,3-diene, as synthetic equivalent of the corresponding unknown alpha-formylimine, has been developed.

  DOI：

  10.1016/s0040-4039(00)74892-1

文献信息

• Useful Dual Diels–Alder Behavior of 2-Azetidinone-Tethered Aryl Imines as Azadienophiles or Azadienes: A -Lactam-Based Stereocontrolled Access to Optically Pure Highly Functionalized Indolizidine Systems
  作者：Benito Alcaide、Pedro Almendros、Jose M. Alonso、Moustafa F. Aly

  DOI：10.1002/chem.200304712

  日期：2003.7.21

  diene in the presence of different Lewis acids. The effect of the amount of catalyst on the conversion rate as well as on the product ratio has been studied. Under standard reaction conditions, indium(III) chloride and zinc(II) iodide provided the best yields, and indium(III) triflate the highest diastereoselectivity in the Lewis acid promoted aza-Diels-Alder cycloaddition. Treatment of the aforementioned

  已经发现衍生自4-氧杂氮杂环丁烷-2-甲醛的亚胺是通用的Diels-Alder试剂，因为它们表现出两种反应模式。在不同的路易斯酸存在下，2-氮杂环丁酮系链的亚胺与Danishefsky的二烯进行非对映选择性反应。已经研究了催化剂的量对转化率以及产物比率的影响。在标准反应条件下，氯化铟（III）和碘化锌（II）提供的收率最高，而三氟甲磺酸铟（IIIflate）在路易斯酸中促进的氮杂-狄尔斯-阿尔德环加成反应的非对映选择性最高。用环戊二烯，2,3-二甲基-1,3-丁二烯或3处理上述亚胺，4-二氢-2 H-吡喃导致由反电子需求缩合产生的环加合物，其中涉及β-内酰胺系的芳基亚胺作为杂二烯组分。另外，已经开发了从β-内酰胺制备吲哚并立定的第一种方法。该过程涉及伴随有环化作用的氮杂-Diels-Alder环加合物中β-内酰胺环的酰胺键裂解。当与对映体纯的底物进行反应时，发生完全手性转移。
• 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。
• Rapid and Stereocontrolled Synthesis of Racemic and Optically Pure Highly Functionalized Pyrrolizidine Systems via Rearrangement of 1,3-Dipolar Cycloadducts Derived from 2-Azetidinone-Tethered Azomethine Ylides
  作者：Benito Alcaide、Pedro Almendros、Jose M. Alonso、Moustafa F. Aly

  DOI：10.1021/jo005686s

  日期：2001.2.1

  a convenient procedure for the straightforward preparation of polyfunctionalized enantiopure pyrrolizidine systems. The methodology capitalizes on a HCl(g)-promoted reaction of the 1,3-dipolar cycloadducts derived from 2-azetidinone-tethered azomethine ylides, smoothly affording different types of highly functionalized bi- and tricyclic systems in racemic and optically pure forms. This process involves

  这项工作描述了一种方便的方法，可以直接制备多官能化对映体纯的吡咯嗪烷体系。该方法利用了由HCl（g）促进的由2-氮杂环丁酮拴住的偶氮甲亚胺衍生的1,3-偶极环加合物的反应，可顺利提供消旋和光学纯净形式的不同类型的高度官能化的双环和三环系统。该过程涉及四元环的选择性键裂解，然后在反应条件下重排。已证明所采用的合成途径与多种4-氧杂氮杂环丁烷-2-甲醛，α-氨基酯或偶极亲和性相容，为吡咯烷酮系统提供了通用的入口。
• Stereoselective synthesis of 5-(41-azetidinyl)-proline esters via 1,3-dipolar cycloaddition reaction of N-metalated azomethine ylides
  作者：G Subramaniyan、R Raghunathan、Ana M Martin Castro

  DOI：10.1016/s0040-4020(02)01521-1

  日期：2003.1

  (E)-3-arylidene-4-chromanones undergo regioselective 1,3-dipolar cycloaddition reaction with N-metalated azomethine ylides derived from β-lactam imines of glycine methyl ester in the presence of silver acetate to give spiropyrrolidines in moderate to good yield. The regio and stereochemistry of the cycloadducts have been established by single crystal X-ray structure and spectroscopic techniques.

  构象锁定的小号-反本烯酮功能在（ë）-3-亚芳基-4-苯并二氢吡喃酮类经历区域选择性1,3-偶极环加成反应用ñ -metalated从甘氨酸甲酯的β内酰胺亚胺在存在衍生甲亚胺叶立德用乙酸银制得螺吡咯烷，产率中等至良好。环加合物的区域和立体化学已经通过单晶X射线结构和光谱技术确定。
• Enantioselective Synthesis of<i>cis</i>-4-Formyl-β-lactams<i>via</i>Chiral N-Heterocyclic Carbene-Catalyzed Kinetic Resolution
  作者：Gong-Qiang Li、Yi Li、Li-Xin Dai、Shu-Li You

  DOI：10.1002/adsc.200800071

  日期：2008.6.9

  An efficient synthesis of optically pure cis-4-formyl-β-lactams (up to 99% ee) by a chiral NHC-catalyzed ring expansion reaction has been realized, featuring the ready availability of both the substrate and the catalyst, and the mild reaction conditions. The current method is also suitable for the synthesis of enantioenriched 4-formyl-β-lactams and succinimides containing quaternary carbon centers

  通过手性NHC催化的扩环反应，可以高效合成光学纯的顺式-4-甲酰基-β-内酰胺（最高ee达99％），具有容易获得的底物和催化剂，并且温和的特点反应条件。当前的方法也适用于合成富含对映体的4-甲酰基-β-内酰胺和含有季碳中心的琥珀酰亚胺。