(4S)-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-(2-propynyl)-azetidine-2,3-dione | 252045-70-8

• 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-propynyl)-azetidine-2,3-dione
• 英文别名: 4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-(2-propynyl)-azetidine-2,3-dione；(4S)-4-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-prop-2-ynylazetidine-2,3-dione
• CAS: 252045-70-8
• 化学式: C₁₁H₁₃NO₄
• 分子量: 223.229
• InChiKey: RKFNNXSCGCBNJK-SFYZADRCSA-N

物化性质

• 沸点：
  307.7±52.0 °C(Predicted)
• 密度：
  1.270±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.2
• 重原子数：
  16
• 可旋转键数：
  2
• 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-propynyl)-azetidine-2,3-dione 在 氯化铵 、 镉 作用下， 以 甲醇 为溶剂， 以35%的产率得到(2S)-2-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-2-(prop-2-ynylamino)acetic acid
  参考文献：
  名称：

  A Novel One-Step Approach for the Preparation of α-Amino Acids, α-Amino Amides, and Dipeptides from Azetidine-2,3-diones

  摘要：

  A remarkable reaction of azetidine-2,3-diones with primary as well as secondary amines, and water is presented. Simply by varying the nucleophile, an unprecedented one-step synthesis of alpha-amino acids, alpha-amino amides, and dipeptides, was developed in both the racemic and optically pure forms. The current mechanistic hypothesis invokes a concerted process involving CO extrusion. However, a stepwise pathway can also account for these novel transformations.

  DOI：

  10.1002/1521-3765(20020816)8:16<3646::aid-chem3646>3.0.co;2-m
• 作为产物：
  描述：

  (-)-(3R,4S)-3-acetoxy-4-[(S)-2,2-dimethyl-1,3-dioxolan-4-yl]-1-(2-propynyl)-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-propynyl)-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

• 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 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。
• Indium-Promoted Acyloxyallylation Reaction of Azetidine-2,3-diones in Aqueous Media: A New Route to Densely Functionalized 3-Substituted 3-Hydroxy-β-lactams
  作者：Benito Alcaide、Pedro Almendros、Cristina Aragoncillo、Gema Cabrero、Ricardo Callejo、M. Pilar Ruiz

  DOI：10.1002/ejoc.200800521

  日期：2008.9

  Densely functionalized 3-substituted 3-hydroxy-β-lactams have been obtained by acyloxyallylation reaction of azetidine-2,3-diones with 3-bromopropenyl acetate or benzoate in aqueous media promoted by indium under Barbier conditions. Two new stereocenters were formed; the stereochemistry at the new C-3 quaternary center was fully controlled by placing a bulky chiral substituent at C-4. However, poor

  在巴比尔条件下，通过氮杂环丁烷-2,3-二酮与乙酸3-溴丙烯酯或苯甲酸酯在铟促进的水性介质中的酰氧基烯丙基化反应，得到了密集官能化的3-羟基-β-内酰胺。形成了两个新的立体中心；通过在 C-4 上放置一个庞大的手性取代基，可以完全控制新 C-3 四元中心的立体化学。然而，在形成的新烯丙基立体中心中观察到较差的非对映选择性（高达 58 % de）。（© Wiley-VCH Verlag GmbH & Co. KGaA，69451 Weinheim，德国，2008）
• Metal-Promoted Allylation, Propargylation, or Allenylation of Azetidine-2,3-diones in Aqueous and Anhydrous Media. Application to the Asymmetric Synthesis of Densely Functionalized 3-Substituted 3-Hydroxy-β-lactams
  作者：Benito Alcaide、Pedro Almendros、Cristina Aragoncillo、Raquel Rodríguez-Acebes

  DOI：10.1021/jo015704l

  日期：2001.7.1

  Metal-mediated carbonyl allylation, allenylation, and propargylation of optically pure azetidine-2,3-diones were investigated in both anhydrous and aqueous environments. Different metals promoters showed varied regioselectivities on product formation during allenylation/propargylation reactions of the keto-beta -lactams. The stereochemistry of the new C3-substituted C3-hydroxy quaternary center was controlled by placing a chiral auxiliary at C4. In this way, the coupling of azetidine-2,3-diones with a variety of propenyl-, propynyl-, and allenylmetal reagents offers a convenient asymmetric entry to potentially bioactive 3-substituted 3-hydroxy-beta -lactams.
• Asymmetric synthesis of densely functionalized 3-substituted 3-hydroxy-β-lactams via novel, highly stereoselective Baylis-Hillman and allylation reactions of enantiopure 3-oxo-2-azetidinones
  作者：Benito Alcaide、Pedro Almendros、Cristina Aragoncillo

  DOI：10.1016/s0040-4039(99)01527-0

  日期：1999.10

  New asymmetric routes based on both Baylis-Hillman and allylation reactions of enantiopure 3-oxo-2-azetidinones are used for the highly stereoselective, efficient preparation of densely functionalized 3-substituted 3-hydroxy-beta-lactams. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.