(2RS,5SR)-trans-2,5-dimethyl-1-<1',3'-dioxo-3'-chloro-2'-ethylpropyl>pyrrolidine | 135469-57-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (2RS,5SR)-trans-2,5-dimethyl-1-<1',3'-dioxo-3'-chloro-2'-ethylpropyl>pyrrolidine
• 英文别名: (2RS,5SR)-trans-2,5-dimethyl-1-(1',3'-dioxo-3'-chloro-2'-ethylpropyl)pyrrolidine
• CAS: 135469-57-7；135469-58-8
• 化学式: C₁₁H₁₈ClNO₂
• 分子量: 231.722
• InChiKey: CBZXORNPCMEJFP-ZAZKALAHSA-N

物化性质

• 沸点：
  327.3±25.0 °C(Predicted)
• 密度：
  1.106±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.18
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  37.38
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-mercaptopyridine-1-oxide sodium salt 、 (2RS,5SR)-trans-2,5-dimethyl-1-<1',3'-dioxo-3'-chloro-2'-ethylpropyl>pyrrolidine 以 二氯甲烷 为溶剂， 反应 3.0h， 以86%的产率得到(2-sulfanylidenepyridin-1-yl) 2-[(2R,5R)-2,5-dimethylpyrrolidine-1-carbonyl]butanoate
  参考文献：
  名称：

  Free-radical telomerization of chiral acrylamides: control of stereochemistry in additions and halogen-atom transfer

  摘要：

  The free-radical reactions of carbon radicals substituted alpha to a chiral pyrrolidine amide have been studied. The pyrrolidine used was 2,5-dimethylpyrrolidine, available as either the R,R or S,S enantiomer from D- or L-alanine, and the radicals were generated (1) by tin radical abstraction of the halogen from the 2-iodobutyramide of the pyrrolidine, (2) by decomposition of a pyrrolidine amide substituted Barton ester 4, and (3) by radical addition to the acrylamide of the pyrrolidine 3. Addition of chiral-alpha amide radicals to alkenes occurs with a selectivity of approximately 15:1 at room temperature, while bromine- and iodine-atom transfer to these radicals occurs with a selectivity of 10:1 at room temperature. Telomerization of the acrylamide 3 is achieved by photolysis of BrCCl3 in the presence of acrylamide. Telomers are readily formed and the lower telomers, n = 1 to 5, were isolated and characterized. Halogens were removed from the telomers by reduction with tributyltin hydride and in this way, the major diastereomers of the n = 2 and n = 3 telomers were converted to known compounds. Chain-transfer constants for the BrCCl3 telomerization were determined and they range from 0.3 to 0.5 for C(n) = C2 to C5. An analysis of the chiral amide auxiliary is presented that may prove useful in the consideration of other auxiliary groups.

  DOI：

  10.1021/ja00018a044
• 作为产物：
  描述：

  (2RS,5SR)-trans-2,5-dimethyl-1-<1',3'-dioxo-2'-ethyl-3'-hydroxypropyl>pyrrolidine 在 氯化亚砜 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以84%的产率得到(2RS,5SR)-trans-2,5-dimethyl-1-<1',3'-dioxo-3'-chloro-2'-ethylpropyl>pyrrolidine
  参考文献：
  名称：

  Free-radical telomerization of chiral acrylamides: control of stereochemistry in additions and halogen-atom transfer

  摘要：

  The free-radical reactions of carbon radicals substituted alpha to a chiral pyrrolidine amide have been studied. The pyrrolidine used was 2,5-dimethylpyrrolidine, available as either the R,R or S,S enantiomer from D- or L-alanine, and the radicals were generated (1) by tin radical abstraction of the halogen from the 2-iodobutyramide of the pyrrolidine, (2) by decomposition of a pyrrolidine amide substituted Barton ester 4, and (3) by radical addition to the acrylamide of the pyrrolidine 3. Addition of chiral-alpha amide radicals to alkenes occurs with a selectivity of approximately 15:1 at room temperature, while bromine- and iodine-atom transfer to these radicals occurs with a selectivity of 10:1 at room temperature. Telomerization of the acrylamide 3 is achieved by photolysis of BrCCl3 in the presence of acrylamide. Telomers are readily formed and the lower telomers, n = 1 to 5, were isolated and characterized. Halogens were removed from the telomers by reduction with tributyltin hydride and in this way, the major diastereomers of the n = 2 and n = 3 telomers were converted to known compounds. Chain-transfer constants for the BrCCl3 telomerization were determined and they range from 0.3 to 0.5 for C(n) = C2 to C5. An analysis of the chiral amide auxiliary is presented that may prove useful in the consideration of other auxiliary groups.

  DOI：

  10.1021/ja00018a044