2-(trimethylsilyl)ethyl 3-<1-(tosyloxy)-2-oxo-4-azetidinyl>propionate | 145586-92-1

• 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: 2-(trimethylsilyl)ethyl 3-<1-(tosyloxy)-2-oxo-4-azetidinyl>propionate
• 英文别名: 2-Trimethylsilylethyl 3-[1-(4-methylphenyl)sulfonyloxy-4-oxoazetidin-2-yl]propanoate
• CAS: 145586-92-1
• 化学式: C₁₈H₂₇NO₆SSi
• 分子量: 413.567
• InChiKey: BFEOPMUAVNAVIG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.88
• 重原子数：
  27
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  98.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl 3-<1-(tosyloxy)-2-oxo-4-azetidinyl>propionate 在 三甲基氯硅烷 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 22.0h， 以50%的产率得到2-(trimethylsilyl)ethyl 3-(trans-3-chloro-2-oxo-4-azetidinyl)propionate
  参考文献：
  名称：

  Diastereoselective addition of nucleophiles to the C3 position of N-(tosyloxy)-.beta.-lactams

  摘要：

  trans-3-Substituted-beta-lactams 22a-j are conveniently synthesized by treating 21 with suitable nucleophiles in the presence of Et3N or (i-Pr)2EtN. The key aspects of this method relative to traditional methods are that the C3 position of beta-lactam 21 acts as an electrophilic center and the addition of nucleophiles is accompanied by N-O bond cleavage. The reaction is tolerant of a variety of alkyl groups at the C4 position, although an electron-withdrawing group at C4 is detrimental. The rate of reaction is increased if an electron-withdrawing group is present at the C3 position. Base-initiated enolization followed by an S(N)2' displacement of tosylate by a nucleophile is mechanistically consistent with these observations, but enolization is considered to be the rate-determining step. Suitable sources of nucleophiles are TMSX, Et3NH.X, or (i-Pr)2EtNH.X, while Bu4N.X or LiX initiates the formation of a byproduct, 31. Triethylamine has been found to act as a competitive nucleophile to form 30 and therefore was not the preferred base for the reaction. The yield of product can bc optimized by using a non-nucleophilic base, such as (i-Pr)2EtN, and an excess of nucleophile.

  DOI：

  10.1021/ja00055a026
• 作为产物：
  描述：

  2-(Trimethylsilyl)ethyl 3-(1-hydroxy-2-oxo-4 azetidinyl)propionate 、 对甲苯磺酰氯 在 三乙胺 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以90%的产率得到2-(trimethylsilyl)ethyl 3-<1-(tosyloxy)-2-oxo-4-azetidinyl>propionate
  参考文献：
  名称：

  Diastereoselective addition of nucleophiles to the C3 position of N-(tosyloxy)-.beta.-lactams

  摘要：

  trans-3-Substituted-beta-lactams 22a-j are conveniently synthesized by treating 21 with suitable nucleophiles in the presence of Et3N or (i-Pr)2EtN. The key aspects of this method relative to traditional methods are that the C3 position of beta-lactam 21 acts as an electrophilic center and the addition of nucleophiles is accompanied by N-O bond cleavage. The reaction is tolerant of a variety of alkyl groups at the C4 position, although an electron-withdrawing group at C4 is detrimental. The rate of reaction is increased if an electron-withdrawing group is present at the C3 position. Base-initiated enolization followed by an S(N)2' displacement of tosylate by a nucleophile is mechanistically consistent with these observations, but enolization is considered to be the rate-determining step. Suitable sources of nucleophiles are TMSX, Et3NH.X, or (i-Pr)2EtNH.X, while Bu4N.X or LiX initiates the formation of a byproduct, 31. Triethylamine has been found to act as a competitive nucleophile to form 30 and therefore was not the preferred base for the reaction. The yield of product can bc optimized by using a non-nucleophilic base, such as (i-Pr)2EtN, and an excess of nucleophile.

  DOI：

  10.1021/ja00055a026

文献信息

• Functionalization of the .beta.-lactam ring: diastereoselective azide transfer and nitrogen-oxygen bond reduction on C4 substituted N-hydroxy-.beta.-lactams in one step
  作者：Catherine M. Gasparski、Min Teng、Marvin J. Miller

  DOI：10.1021/ja00033a072

  日期：1992.3
• Diastereoselective addition of nucleophiles to the C3 position of N-(tosyloxy)-.beta.-lactams
  作者：Min Teng、Marvin J. Miller

  DOI：10.1021/ja00055a026

  日期：1993.1

  trans-3-Substituted-beta-lactams 22a-j are conveniently synthesized by treating 21 with suitable nucleophiles in the presence of Et3N or (i-Pr)2EtN. The key aspects of this method relative to traditional methods are that the C3 position of beta-lactam 21 acts as an electrophilic center and the addition of nucleophiles is accompanied by N-O bond cleavage. The reaction is tolerant of a variety of alkyl groups at the C4 position, although an electron-withdrawing group at C4 is detrimental. The rate of reaction is increased if an electron-withdrawing group is present at the C3 position. Base-initiated enolization followed by an S(N)2' displacement of tosylate by a nucleophile is mechanistically consistent with these observations, but enolization is considered to be the rate-determining step. Suitable sources of nucleophiles are TMSX, Et3NH.X, or (i-Pr)2EtNH.X, while Bu4N.X or LiX initiates the formation of a byproduct, 31. Triethylamine has been found to act as a competitive nucleophile to form 30 and therefore was not the preferred base for the reaction. The yield of product can bc optimized by using a non-nucleophilic base, such as (i-Pr)2EtN, and an excess of nucleophile.