(-)-(4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-(2-propenyl)-azetidine-2,3-dione | 252045-68-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-(4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-(2-propenyl)-azetidine-2,3-dione
• 英文别名: 4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-(2-propenyl)-azetidine-2,3-dione；(4S)-4-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-prop-2-enylazetidine-2,3-dione
• CAS: 252045-68-4
• 化学式: C₁₁H₁₅NO₄
• 分子量: 225.244
• InChiKey: UNOCWZITPNQZOY-SFYZADRCSA-N

物化性质

• 沸点：
  302.2±52.0 °C(Predicted)
• 密度：
  1.204±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (-)-(4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-(2-propenyl)-azetidine-2,3-dione 在 氯化铵 、 锌 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 30.0h， 生成 (-)-(3R,4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-3-hydroxy-1-(2-propynyl)-3-(2-propynyl)-2-azetidinone
  参考文献：
  名称：

  Regio- and Stereocontrolled Metal-Mediated Carbonyl Propargylation or Allenylation of Enantiomerically Pure Azetidine-2,3-diones:  Synthesis of Highly Functionalized 3-Substituted 3-Hydroxy-β-lactams

  摘要：

  Regio and stereocontrolled metal-mediated Barbier-type reactions of azetidine-2,3-diones with differently substituted propargyl bromides offer an efficient asymmetric entry to densely functionalized 3-propargyl- (or allenyl-) substituted 3-hydroxy-beta-lactams.

  DOI：

  10.1021/ol005736f
• 作为产物：
  描述：

  (-)-(3R,4S)-3-acetoxy-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-(2-propenyl)-2-azetidinone 在 草酰氯 、 sodium methylate 、 二甲基亚砜 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.33h， 生成 (-)-(4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-(2-propenyl)-azetidine-2,3-dione
  参考文献：
  名称：

  Metal-Mediated Carbonyl-1,3-butadien-2-ylation by 1,4-Bis(methanesulfonyl)-2-butyne or 1,4-Dibromo-2-butyne in Aqueous Media:  Asymmetric Synthesis of 3-Substituted 3-Hydroxy-β-lactams

  摘要：

  Metal-mediated 1,3-butadien-2-ylation reactions between 1,4-dibromo-2-butyne or 1,4-bis(methanesulfonyl)-2-butyne and optically pure azetidine-2,3-diones were investigated in aqueous media, offering a convenient asymmetric entry to the potentially bioactive 3-substituted 3-hydroxy-beta-lactam moiety. The diastereoselectivity of the addition reaction was controlled by the bulky chiral auxiliary at C4. However, while the regioselectivity of the process was full, the chemical yield of the addition was a function of the nature of both the metal reagent and the system solvent as well. In addition, 2-azetidinone-tethered 1,3-butadienes can easily be transformed into other functionalities via Diels-Alder reaction.

  DOI：

  10.1021/jo016247b

文献信息

• Stereoselective NaN3-catalyzed halonitroaldol-type reaction of azetidine-2,3-diones in aqueous media
  作者：Benito Alcaide、Pedro Almendros、Amparo Luna、M. Rosario Torres

  DOI：10.1039/b802011f

  日期：——

  Azetidine-2,3-diones (α-oxo-β-lactams) and bromonitromethane undergo coupling in aqueous media in the presence of catalytic amounts of sodium azide. The stereoselectivity of the process was generally good, proceeding with reasonable anti : syn ratios under substrate control. On this basis, a simple and fast protocol for the synthesis of the potentially bioactive 3-substituted 3-hydroxy-β-lactam moiety has been developed. Besides, 2-azetidinone-tethered 1-halo-1-nitroalkan-2-ols are quite useful building blocks; for example, reactions of the above nitrobromohydrins provided spiranic and fused bicyclic-β-lactams.

  乙基丁二酸二酮（α-氧代-β-内酰胺）和溴硝基甲烷在催化量的叠氮化钠存在下，在水介质中发生偶联反应。该过程的立体选择性通常良好，在底物控制下能获得合理的反式：顺式比率。基于此，我们开发了一种简便快捷的方法来合成潜在生物活性的3-取代-3-羟基-β-内酰胺片段。此外，2-吖丁啶酮连接的1-卤代-1-硝基烷-2-醇是非常有用的构建单元；例如，上述硝基溴氢醇的反应提供了螺旋内酰胺和稠合双环-β-内酰胺。
• Straightforward Asymmetric Entry to Highly Functionalized 3-Substituted 3-Hydroxy-β-lactams via Baylis−Hillman or Bromoallylation Reactions
  作者：Benito Alcaide、Pedro Almendros、Cristina Aragoncillo、Raquel Rodríguez-Acebes

  DOI：10.1021/jo035472l

  日期：2004.2.1

  The reaction of various activated vinyl systems, including 2-cyclopenten-1-one, with enantiopure azetidine-2,3-diones 1 was promoted by DABCO to afford the corresponding optically pure Baylis−Hillman adducts 2 without detectable epimerization. However, the reaction of α-keto lactams 1 with but-3-yn-2-one was not as successful, giving the corresponding β-halo Baylis−Hillman adduct in low yield. Metal-mediated

  DABCO促进了各种活化的乙烯基系统（包括2-环戊烯-1-酮）与对映体纯的氮杂环丁烷2,3-二酮1的反应，得到了相应的光学纯的Baylis-Hillman加合物2，而没有可检测的差向异构化。然而，α-酮内酰胺1与but-3-yn-2-one的反应不那么成功，从而以低收率得到了相应的β-卤代Baylis-Hillman加合物。在水介质中研究了金属介导的2，3-二溴丙烯与氮杂环丁烷-2，3-二酮1之间的溴代烯丙基化反应。令人惊讶地，铟不能促进α-酮内酰胺1的溴代烯丙基化反应，但是Sn-Hf 4 Cl促进了酮1的溴代烯丙基化。高效地进行了操作，以得到作为单一非对映异构体的溴高烯丙基醇5。在此基础上，开发了用于潜在生物活性的3个取代的3-羟基-β-内酰胺部分的不对称合成的简单快速的方法。
• New Regiocontrolled Synthesis of Functionalized Pyrroles from 2-Azetidinone-Tethered Allenols
  作者：Benito Alcaide、Pedro Almendros、Rocío Carrascosa、María C. Redondo

  DOI：10.1002/chem.200700788

  日期：2008.1.7

  A new one-pot approach to synthesize densely substituted racemic and enantiopure pyrroles from beta-lactams has been developed. The approach relies on the regiocontrolled cyclization of beta-allenamine intermediates derived from the ring opening of 2-azetidinone-tethered allenols. In this approach four points of diversity are introduced, one of which is the position of the allene moiety on the beta-lactam

  已开发出一种新的一锅法，可从β-内酰胺合成密集取代的外消旋和对映纯吡咯。该方法依赖于衍生自2-氮杂环丁酮系链的烯丙醇的开环的β-亚胺胺中间体的区域控制环化。在这种方法中，引入了四个多样性点，其中之一是β-内酰胺环上丙二烯部分的位置。
• New Aspects of the Indium Chemistryof Carbonyl-β-lactams
  作者：Benito Alcaide、Pedro Almendros、Cristina Aragoncillo、Raquel Rodríguez-Acebes

  DOI：10.1055/s-2003-39388

  日期：——

  Reactions of racemic as well as optically pure carbonyl-β-lactams with stabilized organo-indium reagents were investigated in aqueous media. The regio- and stereochemistry of the processes were generally good, offering a convenient asymmetric entry to densely functionalized hydroxy-β-lactams.

  研究了外消旋和光学纯羰基-δ-内酰胺与稳定的有机铟试剂在水介质中的反应。反应过程的区域和立体化学性质普遍良好，为获得官能化程度较高的羟基δ-内酰胺提供了便捷的不对称途径。
• Organocatalyzed Three-Component Ugi and Passerini Reactions of 4-Oxoazetidine-2-carbaldehydes and Azetidine-2,3-diones. Application to the Synthesis of γ-Lactams and γ-Lactones
  作者：Benito Alcaide、Pedro Almendros、Cristina Aragoncillo、Ricardo Callejo、M. Pilar Ruiz

  DOI：10.1021/jo4015358

  日期：2013.10.18

  P-3CR adducts have been obtained in good yields and reasonable diastereoselectivities. Phenyl phosphinic acid has been the catalyst of choice to study the scope of both organocatalyzed multicomponent reactions using a variety of β-lactams, isocyanides, and amines. Highly functionalized U-3CR and P-3CR adducts derived from β-lactams have proved to be useful substrates for the preparation of enantiopure γ-lactams

  研究了4-氧杂氮杂环丁烷-2-甲醛的有机催化U-3CR。另外，首次描述了4-氧杂氮杂环丁烷-2-甲醛和氮杂环丁烷-2，3-二酮的有机催化的P-3CR。已以良好的收率和合理的非对映选择性获得了U-3CR和P-3CR加合物。苯次膦酸一直是研究使用多种β-内酰胺，异氰酸酯和胺的有机催化多组分反应范围的选择催化剂。事实证明，衍生自β-内酰胺的高度官能化的U-3CR和P-3CR加合物是在酸性或碱性条件下通过N1-C2β-内酰胺开环/环化制备对映体纯的γ-内酰胺和γ-内酯的有用底物。