trans-1-tert-Butyl-3-(N,N-diethylamino)-4-(N-tert-butyliminomethyl)-2-azetidinone | 135613-82-0

• 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-(N-tert-butyliminomethyl)-2-azetidinone
• 英文别名: (3S,4R)-1-tert-butyl-4-(tert-butyliminomethyl)-3-(diethylamino)azetidin-2-one
• CAS: 135613-82-0
• 化学式: C₁₆H₃₁N₃O
• 分子量: 281.442
• InChiKey: VKQFTWUEVHKYSQ-STQMWFEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  35.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-二乙基氨基乙酸乙酯 、 N-tert-Butyl-N'-[2,2-dimethyl-prop-(E)-ylidene]-formamidine 生成 cis-1-tert-Butyl-3-(N,N-diethylamino)-4-(N-tert-butyliminomethyl)-2-azetidinone 、 trans-1-tert-Butyl-3-(N,N-diethylamino)-4-(N-tert-butyliminomethyl)-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

• 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.