1-(tert-butyl) 2-methyl (2S,5S)-5-((triisopropylsilyl)ethynyl)pyrrolidine-1,2-dicarboxylate | 1195748-63-0

• 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: 1-(tert-butyl) 2-methyl (2S,5S)-5-((triisopropylsilyl)ethynyl)pyrrolidine-1,2-dicarboxylate
• 英文别名: 1-(tert-butyl) 2-methyl (2S)-5-((triisopropylsilyl)ethynyl)pyrrolidine-1,2-dicarboxylate
• CAS: 1195748-63-0
• 化学式: C₂₂H₃₉NO₄Si
• 分子量: 409.641
• InChiKey: POCZKKUNEGARBJ-OALUTQOASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.15
• 重原子数：
  28.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  55.84
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  (S)-1-tert-butyl 2-methyl 5-((triisopropylsilyl)ethynyl)-2,3-dihydro-1H-pyrrole-1,2-dicarboxylate 在 三乙基硅烷 、 三氟乙酸 作用下， 以 甲苯 为溶剂， 生成 1-(tert-butyl) 2-methyl (2S,5S)-5-((triisopropylsilyl)ethynyl)pyrrolidine-1,2-dicarboxylate 、 1-(tert-butyl) 2-methyl (2S,5R)-5-((triisopropylsilyl)ethynyl)pyrrolidine-1,2-dicarboxylate
  参考文献：
  名称：

  Development of a Scalable Synthesis of Dipeptidyl Peptidase-4 Inhibitor ABT-279

  摘要：

  A convergent, scalable Synthesis of dipeptidyl peptidase-4 inhibitor, ABT-279, has been developed and demonstrated on multikilogram scale. The cis-2,5-disubstituted pyrrolidine is generated by cyclization of a Boc-amine onto an alkynyl ketone followed by stereospecific reduction of the resulting acyliminium intermediate. The amine coupling partner was prepared by a novel Hofmann rearrangement promoted by 1,3-dibromo-5,5-dimethylhydantoin. The final product was isolated as the L-malic acid salt. The scale-up campaign consisted of 15 steps and delivered 42 kg of ABT-279 in 14% overall yield. A second-generation Synthesis that addresses some of the issues encountered during scale-up was developed and demonstrated on kilogram scale.

  DOI：

  10.1021/op900197r

文献信息

• Visible Light-Induced Direct S₀ → T_<i>n</i> Transition of Benzophenone Promotes C(sp³)–H Alkynylation of Ethers and Amides
  作者：Koki Matsumoto、Masaya Nakajima、Tetsuhiro Nemoto

  DOI：10.1021/acs.joc.0c01573

  日期：2020.9.18

  Benzophenone has an S-0 -> S-1 absorption band at 365 nm. However, the rarely reported S-0 -> T-n transition occurs upon irradiation at longer wavelengths. Herein, we employed benzophenone as a catalyst and exploited its S-0 -> T-n transition in C(sp(3))-H alkynylations with hypervalent iodine reagents. The selective benzophenone excitation prevented alkynylating reagent decomposition, enabling the reaction to proceed under mild conditions. The reaction mechanism was investigated by spectroscopic and computational studies.