trans-1-tert-Butyl-3-(N,N-diethylamino)-4-(2-pyridyl)-2-azetidinone | 133693-65-9

• 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: trans-1-tert-Butyl-3-(N,N-diethylamino)-4-(2-pyridyl)-2-azetidinone
• 英文别名: (3R,4S)-1-tert-butyl-3-(diethylamino)-4-pyridin-2-ylazetidin-2-one
• CAS: 133693-65-9
• 化学式: C₁₆H₂₅N₃O
• 分子量: 275.394
• InChiKey: HCLXAQWGQMYXNM-ZIAGYGMSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  36.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (E)-N-(pyridin-2-ylmethylene)tert-butylamine 、 2-二乙基氨基乙酸乙酯 在 zinc(II) chloride 、 lithium diisopropyl amide 作用下， 生成 trans-1-tert-Butyl-3-(N,N-diethylamino)-4-(2-pyridyl)-2-azetidinone
  参考文献：
  名称：

  Stereoselective synthesis of cis- and trans-.beta.-lactams via .alpha.-amino ester enolates and 1-aza-4-hetero-1,3-butadiene systems. Molecular structure of [cyclic] EtOC(O)C(H)(NEt2)C(H)(N(H)-tert-Bu)C(H):N(tert-Bu)ZnCl2: An unexpectedly isolated aldolate

  摘要：

  Lithium and zinc enolates of N,N-diprotected glycine esters 1 react with 1-aza-4-hetero-1,3-butadiene systems 4 selectively affording cis- and trans-3-amino-4-functionalized-2-azetidinones in excellent yields, respectively. The reactions with 1,4-diaza-1,3-butadiene systems are far more selective (de greater-than-or-equal-to 90%) than those with 1-aza-4-oxo- and 1-aza-4-thio-1,3-butadiene systems (de 0-85%). In apolar solvents some of the reactions between the zinc enolates 2 and functionalized imines 4 partly stop at the stage of the C-C coupled product, probably because the metal center migrates to a chelating position between the nitrogen and the hetero atom of the imine. Consequently, elimination of the metal alkoxide and ring closure to a 2-azetidinone product is not likely to occur anymore. This view is supported by the isolation and structural characterization of a ZnCl2 complex of a C-C coupled product, erythro-EtOC(O)C(H)(NEt2)C(H) activated (N(H)-t-Bu)C(H) = N(t-Bu)ZnCl2 (8), which furthermore demonstrates that erythro C-C bond formation leads to a trans-2-azetidinone product. In polar solvents the migration of the metal center is prevented and exclusively 2-azetidinone products are isolated.

  DOI：

  10.1021/jo00020a031

文献信息

• Improved synthesis of beta-lactams using a metal compound
  申请人：RIJKSUNIVERSITEIT UTRECHT

  公开号：EP0404267A1

  公开（公告）日：1990-12-27

  A synthesis of trans-β-lactams with an easily convertible group on the C-4 carbon atom of the azetidinone ring comprising a condensation reaction of a metal enolate with an imine with a heterocyclic group or a diimine is provided. Furthermore, new chiral β-lactams and an enantioselective synthesis of β-lactams using a chiral imine or a-diimine are provided. Also new chiral substituted amino propionic ester metal compounds and new chiral amino acid compounds and processes for the preparation thereof are provided.

  提供一种在氮杂环上的C-4碳原子上具有易于转化的基团的转β-内酰胺合成方法，包括金属烯醇与具有杂环基团或二亚胺的亚胺的缩合反应。此外，提供了新的手性β-内酰胺和使用手性亚胺或α-二亚胺的对映选择性合成β-内酰胺。还提供了新的手性取代氨基丙酸酯金属化合物和新的手性氨基酸化合物及其制备方法。
• Stereoselective synthesis of cis- and trans-.beta.-lactams via .alpha.-amino ester enolates and 1-aza-4-hetero-1,3-butadiene systems. Molecular structure of [cyclic] EtOC(O)C(H)(NEt2)C(H)(N(H)-tert-Bu)C(H):N(tert-Bu)ZnCl2: An unexpectedly isolated aldolate
  作者：Fred H. Van der Steen、Henk Kleijn、Anthony L. Spek、Gerard Van Koten

  DOI：10.1021/jo00020a031

  日期：1991.9

  Lithium and zinc enolates of N,N-diprotected glycine esters 1 react with 1-aza-4-hetero-1,3-butadiene systems 4 selectively affording cis- and trans-3-amino-4-functionalized-2-azetidinones in excellent yields, respectively. The reactions with 1,4-diaza-1,3-butadiene systems are far more selective (de greater-than-or-equal-to 90%) than those with 1-aza-4-oxo- and 1-aza-4-thio-1,3-butadiene systems (de 0-85%). In apolar solvents some of the reactions between the zinc enolates 2 and functionalized imines 4 partly stop at the stage of the C-C coupled product, probably because the metal center migrates to a chelating position between the nitrogen and the hetero atom of the imine. Consequently, elimination of the metal alkoxide and ring closure to a 2-azetidinone product is not likely to occur anymore. This view is supported by the isolation and structural characterization of a ZnCl2 complex of a C-C coupled product, erythro-EtOC(O)C(H)(NEt2)C(H) activated (N(H)-t-Bu)C(H) = N(t-Bu)ZnCl2 (8), which furthermore demonstrates that erythro C-C bond formation leads to a trans-2-azetidinone product. In polar solvents the migration of the metal center is prevented and exclusively 2-azetidinone products are isolated.