trans-1-Benzyl-3-vinyl-4-phenyl-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: trans-1-Benzyl-3-vinyl-4-phenyl-2-azetidinone
• 英文别名: trans-1-benzyl-4-phenyl-3-vinylazetidin-2-one；(3R,4S)-1-benzyl-3-ethenyl-4-phenylazetidin-2-one
• 化学式: C₁₈H₁₇NO
• 分子量: 263.339
• InChiKey: RMFGKQWSMABWAV-IAGOWNOFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  trans-1-Benzyl-3-vinyl-4-phenyl-2-azetidinone 在 palladium on activated charcoal 甲酸铵 作用下， 以 乙二醇 为溶剂， 以83%的产率得到2,N-Dibenzyl-butyramide
  参考文献：
  名称：

  Microwave-Assisted Rapid and Simplified Hydrogenation^1,

  摘要：

  Catalytic transfer hydrogenation has been conducted under microwave irradiation in open vessels using high-boiling solvents such as ethylene glycol (bp 198 degrees C) as the microwave energy transfer agent. Reduction of double bonds and hydrogenolysis of several functional groups were carried out safely and rapidly (3-5 min) at about 110-130 degrees C with 10% Pd/C as an efficient catalyst and ammonium formate as the hydrogen donor. Diverse types of beta-lactam synthons were prepared by the reduction of ring substituents containing alkene and alkylidene groups or conjugated unsaturated esters, Cleavage of the beta-lactam ring by hydrogenolysis of the N-C-4 bond of 4-aryl-2-azetidinones was a facile reaction with 10% Pd/C as the catalyst; but no ring scission occurred when Raney nickel catalyst was employed. Dehalogenation of aromatic compounds was also successful with ammonium formate and Pd/C catalyst. Hydrogenolysis of phenylhydrazone of methyl benzoylformate gave the methyl ester of phenylglycine in excellent yield. The techniques described here for microwave assisted hydrogenation are safe, rapid, and efficient and are suitable for research investigation as well as for undergraduate and high school laboratory exercises.

  DOI：

  10.1021/jo981516s
• 作为产物：
  描述：

  左旋苯甘氨酸 在 titanium(IV) isopropylate 、 iron(III) chloride 、 三甲基氯硅烷 、 乙烯 、 异丙基氯化镁 、 potassium carbonate 作用下， 以 四氢呋喃 、 乙醚 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 3.0h， 生成 trans-1-Benzyl-3-vinyl-4-phenyl-2-azetidinone
  参考文献：
  名称：

  1,2-二氢吡啶-3--3-酮的光化学转化：原始串联逆向[4 + 2] / [2 + 2]环加成过程

  摘要：

  N-苄基-2-苯基-1,2-二氢吡啶-3-酮的紫外线照射提供了主要结构异构体反式-1-苄基-4-苯基-3-乙烯基氮杂环丁酮-2-酮。提出了一种新的串联机制，该机制涉及[4 + 2]光环还原，然后进行Staudinger环加成反应，并受到其他亚胺捕获所谓的乙烯酮中间体的支持。该过程在乙烯的存在下占优势，排除了分子间[2 + 2]环丁烷加合物的形成。

  DOI：

  10.1016/j.tetlet.2013.03.081

文献信息

• The Stereoselective Synthesis of Alkenyl-β-lactams by Palladium-Catalyzed [2+2] Carbonylative Cycloaddition
  作者：Luigino Troisi、Luisella De Vitis、Catia Granito、Erbana Epifani

  DOI：10.1002/ejoc.200300667

  日期：2004.3

  Allyl halides of different structures, under CO pressure, in the presence of Et3N, a catalytic amount of Pd(OAc)2, and triphenylphosphane as ligand, undergo a [2+2] cycloaddition reaction with various imines. The reaction is highly regio- and stereoselective: β-lactams are formed in good yields and with trans diastereoselectivity in both the β-lactam ring and the vinylic moiety. New and important information

  不同结构的烯丙基卤在 CO 压力下，在 Et3N、催化量的 Pd(OAc)2 和作为配体的三苯基膦存在下，与各种亚胺发生 [2+2] 环加成反应。该反应具有高度的区域选择性和立体选择性：β-内酰胺以良好的产率形成，并且在 β-内酰胺环和乙烯基部分均具有反式非对映选择性。建议了关于已知反应机理的新的和重要的信息。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Palladium-Catalyzed Carbonylative [2 + 2] Cycloaddition for the Stereoselective Synthesis of Either cis- or trans-3-Alkenyl .beta.-Lactams
  作者：Hideo Tanaka、A. K. M. Abdul Hai、Masahiro Sadakane、Hiroshi Okumoto、Sigeru Torii

  DOI：10.1021/jo00090a023

  日期：1994.6

  A new potential alkenylketene equivalent, prepared without use of a carboxylic acid or an activated derivative, has been exploited. Palladium-catalyzed carbonylation of an allyl phosphate in the presence of an imine and a tertiary amine under CO pressure (30 kg cm(-2)) stereoselectively gave either a cis-or trans-3-alkenyl beta-lactam in high yield. The stereochemical outcome strongly depends on the nature of the imine employed. Imines conjugated with a carbonyl such as a ketone or an ester stereoselectively produce cis-beta-lactams at room temperature, whereas imines unconjugated with a carbonyl group exclusively afford trans-beta-lactams at 70 degrees C.
• Carbonylative [2+2] cycloaddition for the construction of β-lactam skeleton with palladium catalyst
  作者：Sigeru Torii、Hiroshi Okumoto、Masahiro Sadakane、A.K.M.Abdul Hai、Hideo Tanaka

  DOI：10.1016/0040-4039(93)88102-o

  日期：1993.10

  Palladium-catalyzed carbonylation of allyl diethyl phosphate in the presence of imines under CO pressure (30 Kgcm-2) gave highly stereoselectively either cis- or trans-3-vinyl-beta-lactam compounds, depending on the nature of the imines employed, in high yields.
• Microwave-Assisted Rapid and Simplified Hydrogenation¹^,
  作者：Bimal K. Banik、Khaled J. Barakat、Dilip R. Wagle、Maghar S. Manhas、Ajay K. Bose

  DOI：10.1021/jo981516s

  日期：1999.8.1

  Catalytic transfer hydrogenation has been conducted under microwave irradiation in open vessels using high-boiling solvents such as ethylene glycol (bp 198 degrees C) as the microwave energy transfer agent. Reduction of double bonds and hydrogenolysis of several functional groups were carried out safely and rapidly (3-5 min) at about 110-130 degrees C with 10% Pd/C as an efficient catalyst and ammonium formate as the hydrogen donor. Diverse types of beta-lactam synthons were prepared by the reduction of ring substituents containing alkene and alkylidene groups or conjugated unsaturated esters, Cleavage of the beta-lactam ring by hydrogenolysis of the N-C-4 bond of 4-aryl-2-azetidinones was a facile reaction with 10% Pd/C as the catalyst; but no ring scission occurred when Raney nickel catalyst was employed. Dehalogenation of aromatic compounds was also successful with ammonium formate and Pd/C catalyst. Hydrogenolysis of phenylhydrazone of methyl benzoylformate gave the methyl ester of phenylglycine in excellent yield. The techniques described here for microwave assisted hydrogenation are safe, rapid, and efficient and are suitable for research investigation as well as for undergraduate and high school laboratory exercises.
• Photochemical transformation of a 1,2-dihydropyridin-3-one: an original tandem retro-[4+2]/[2+2] cycloaddition process
  作者：David J. Aitken、Angelo Frongia、Xavier Gaucher、Jean Ollivier、Hummera Rafique、Carlo Sambiagio、Francesco Secci

  DOI：10.1016/j.tetlet.2013.03.081

  日期：2013.5

  2-dihydropyridin-3-one furnished trans-1-benzyl-4-phenyl-3-vinylazetidin-2-one, a structural isomer, as the main product. A novel tandem mechanism involving a [4+2] photocycloreversion followed by a Staudinger cycloaddition reaction is proposed, and is supported with the trapping of the purported vinylketene intermediate by other imines. This process predominates in the presence of ethylene, precluding the formation

  N-苄基-2-苯基-1,2-二氢吡啶-3-酮的紫外线照射提供了主要结构异构体反式-1-苄基-4-苯基-3-乙烯基氮杂环丁酮-2-酮。提出了一种新的串联机制，该机制涉及[4 + 2]光环还原，然后进行Staudinger环加成反应，并受到其他亚胺捕获所谓的乙烯酮中间体的支持。该过程在乙烯的存在下占优势，排除了分子间[2 + 2]环丁烷加合物的形成。