3-tert.butoxycarbonyl-4,4-dimethylazetidino<3,2-d>thiazolidin-2-one | 5317-21-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 3-tert.butoxycarbonyl-4,4-dimethylazetidino<3,2-d>thiazolidin-2-one
• 英文别名: 3-Carbo-tert-butoxy-4,4-dimethylazetidino<3,2-d>thiazolidin-2-on；(1R)-3,3-dimethyl-7-oxo-(1rH,5cH)-4-thia-2,6-diaza-bicyclo[3.2.0]heptane-2-carboxylic acid tert-butyl ester；tert-butyl (1R,5R)-3,3-dimethyl-7-oxo-4-thia-2,6-diazabicyclo[3.2.0]heptane-2-carboxylate
• CAS: 5317-21-5；21138-06-7；26532-35-4
• 化学式: C₁₁H₁₈N₂O₃S
• 分子量: 258.342
• InChiKey: SDXWCFRMGVUNER-HTRCEHHLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  83.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 3-tert.butoxycarbonyl-4,4-dimethylazetidino<3,2-d>thiazolidin-2-one 以 吡啶 为溶剂， 生成 (1R)-6-acetyl-3,3-dimethyl-7-oxo-(1rH,5cH)-4-thia-2,6-diaza-bicyclo[3.2.0]heptane-2-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  青霉素向头孢菌素的转化

  摘要：

  AbstractA new method for the degradation of the thiazolidine ring in penicillins is described. Penicillin V (8a), penicillin G (8b) and 6‐t‐butoxycarbonylaminopenicillanic acid (33) (BOC‐6‐APA) were converted via their acylazides and isocyanates (10 and 34) into 2,2,2‐trichloroethyl urethanes (11 and 35). Reductive removal of the trichloroethoxycarbonyl groups in an aqueous medium gave the 3‐hydroxy‐penam‐derivatives 13 and 36. The structure and various reactions of these carbinolamides are discussed in detail. An oxidative radical fragmentation (using lead tetraacylates and light) followed by thermal treatment transformed the 3‐hydroxy‐penam‐derivatives into the N‐formyl‐β‐lactam‐thio‐enolethers 27 and 37 in which the formyl group could be replaced by hydrogen. Reactions of the β‐lactam and thio‐enolether functions are described.The BOC‐derivative 37 can be transformed into the isomeric compound 3, an intermediate in Woodward's total synthesis of cephalosporins.

  DOI：

  10.1002/hlca.19720550209
• 作为产物：
  描述：

  4,4-Dimethylazetidino<3,2-d>thiazolidin-2-on 在 calcium carbonate 作用下， 以 四氢呋喃 为溶剂， 生成 3-tert.butoxycarbonyl-4,4-dimethylazetidino<3,2-d>thiazolidin-2-one
  参考文献：
  名称：

  青霉素向头孢菌素的转化

  摘要：

  AbstractA new method for the degradation of the thiazolidine ring in penicillins is described. Penicillin V (8a), penicillin G (8b) and 6‐t‐butoxycarbonylaminopenicillanic acid (33) (BOC‐6‐APA) were converted via their acylazides and isocyanates (10 and 34) into 2,2,2‐trichloroethyl urethanes (11 and 35). Reductive removal of the trichloroethoxycarbonyl groups in an aqueous medium gave the 3‐hydroxy‐penam‐derivatives 13 and 36. The structure and various reactions of these carbinolamides are discussed in detail. An oxidative radical fragmentation (using lead tetraacylates and light) followed by thermal treatment transformed the 3‐hydroxy‐penam‐derivatives into the N‐formyl‐β‐lactam‐thio‐enolethers 27 and 37 in which the formyl group could be replaced by hydrogen. Reactions of the β‐lactam and thio‐enolether functions are described.The BOC‐derivative 37 can be transformed into the isomeric compound 3, an intermediate in Woodward's total synthesis of cephalosporins.

  DOI：

  10.1002/hlca.19720550209

文献信息

• The conversion of β-amino esters by alkylaluminum compounds into β-lactams
  作者：Helmut Vorbrüggen、Robert Burns Woodward

  DOI：10.1016/s0040-4020(01)80350-1

  日期：——

  β-Amino esters with an unsubstituted amino group such as 1 or 19 can be cyclized by two equivalents of alkylaluminum compounds such as triisobutylaluminum in yields up to 61% to the corresponding β-lactams 2 or 20.

  具有两个未取代氨基的β-氨基酯（例如1或19）可以被两当量的烷基铝化合物（例如三异丁基铝）环化，其收率高达相应β-内酰胺2或20的61％。
• The Total Synthesis of Cephalosporin C¹
  作者：R. B. Woodward、K. Heusler、J. Gosteli、P. Naegeli、W. Oppolzer、R. Ramage、S. Ranganathan、H. Vorbrüggen

  DOI：10.1021/ja00956a051

  日期：1966.2
• Die Umwandlung von Penicillinen in Cephalosporine. Modifikationen von Antibiotika, 3. Mitteilung
  作者：K. Heusler

  DOI：10.1002/hlca.19720550209

  日期：1972.1.31

  AbstractA new method for the degradation of the thiazolidine ring in penicillins is described. Penicillin V (8a), penicillin G (8b) and 6‐t‐butoxycarbonylaminopenicillanic acid (33) (BOC‐6‐APA) were converted via their acylazides and isocyanates (10 and 34) into 2,2,2‐trichloroethyl urethanes (11 and 35). Reductive removal of the trichloroethoxycarbonyl groups in an aqueous medium gave the 3‐hydroxy‐penam‐derivatives 13 and 36. The structure and various reactions of these carbinolamides are discussed in detail. An oxidative radical fragmentation (using lead tetraacylates and light) followed by thermal treatment transformed the 3‐hydroxy‐penam‐derivatives into the N‐formyl‐β‐lactam‐thio‐enolethers 27 and 37 in which the formyl group could be replaced by hydrogen. Reactions of the β‐lactam and thio‐enolether functions are described.The BOC‐derivative 37 can be transformed into the isomeric compound 3, an intermediate in Woodward's total synthesis of cephalosporins.