2-(9H-fluoren-9-ylmethoxycarbonylamino)-4-methylpentanethioic acid S-tert-butyl ester

• 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: 2-(9H-fluoren-9-ylmethoxycarbonylamino)-4-methylpentanethioic acid S-tert-butyl ester
• 英文别名: S-tert-butyl (2S)-2-(9H-fluoren-9-ylmethoxycarbonylamino)-4-methylpentanethioate
• 化学式: C₂₅H₃₁NO₃S
• 分子量: 425.592
• InChiKey: ZMYSARQLCMNPIW-QFIPXVFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  80.7
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  Fmoc-L-亮氨酸 、 叔丁基硫醇 在 molybdenium(VI) dioxodichloride 、 苯甲酸酐 作用下， 以 二氯甲烷 为溶剂， 反应 22.0h， 以96%的产率得到2-(9H-fluoren-9-ylmethoxycarbonylamino)-4-methylpentanethioic acid S-tert-butyl ester
  参考文献：
  名称：

  Nucleophilic Acyl Substitutions of Anhydrides with Protic Nucleophiles Catalyzed by Amphoteric, Oxomolybdenum Species

  摘要：

  [GRAPHICS]Among six different group VIb oxometallic species examined, dioxomolybdenum dichloride and oxomolybdenum tetrachloride were the most efficient catalysts to facilitate nucleophilic acyl substitution (NAS) of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. In contrast to the well-recognized redox chemical behaviors associated with oxomolybdenum(VI) species, the catalytic NAS was unprecedented and tolerates virtually all kinds of functional groups. By using benzoic anhydride as a mediator for in situ generation of an incipient mixed anhydride -MoO2Cl2 adduct with a given functional alkanoic acid, one can achieve oleate, dipeptide, diphenylmethyl, N-Fmoc-alpha-amino, pyruvic, and tert-butylthio ester, N-tert-butylamide, and trityl methacrylate syntheses with appropriate protic nucleophiles. The amphoteric character of the Mo=O unit in oxomolybdenum chlorides was found to be responsible for the catalytic NAS profile as supported by a control NAS reaction of using an authentic adduct-MoOCl2(O-2-CBut)(2) between pivalic anhydride and MoO2Cl2 as the catalyst.

  DOI：

  10.1021/jo048363v

文献信息

• Nucleophilic Acyl Substitutions of Anhydrides with Protic Nucleophiles Catalyzed by Amphoteric, Oxomolybdenum Species
  作者：Chien-Tien Chen、Jen-Huang Kuo、Vijay D. Pawar、Yogesh S. Munot、Shieu-Shien Weng、Cheng-Hsiu Ku、Cheng-Yuan Liu

  DOI：10.1021/jo048363v

  日期：2005.2.1

  [GRAPHICS]Among six different group VIb oxometallic species examined, dioxomolybdenum dichloride and oxomolybdenum tetrachloride were the most efficient catalysts to facilitate nucleophilic acyl substitution (NAS) of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. In contrast to the well-recognized redox chemical behaviors associated with oxomolybdenum(VI) species, the catalytic NAS was unprecedented and tolerates virtually all kinds of functional groups. By using benzoic anhydride as a mediator for in situ generation of an incipient mixed anhydride -MoO2Cl2 adduct with a given functional alkanoic acid, one can achieve oleate, dipeptide, diphenylmethyl, N-Fmoc-alpha-amino, pyruvic, and tert-butylthio ester, N-tert-butylamide, and trityl methacrylate syntheses with appropriate protic nucleophiles. The amphoteric character of the Mo=O unit in oxomolybdenum chlorides was found to be responsible for the catalytic NAS profile as supported by a control NAS reaction of using an authentic adduct-MoOCl2(O-2-CBut)(2) between pivalic anhydride and MoO2Cl2 as the catalyst.