有机合成百科

9-芴基甲氧基羰基保护基 Fmoc Protecting Group

概要

9-芴基甲氧基羰基保护基(9-fluorenylmethyloxycarbonyl, Fmoc)、它经常用于通过氨基甲酸酯形成来保护胺基。
该保护基对酸性条件・氧化条件比较稳定、但是在温和的碱性条件下会发生脱保护。另外在接触还原条件下也容易被脱保护。因此,该保护基与Boc,Cbz保护基具有相辅相成的作用。

在许多应用中,它最常用于肽固相合成方法中。由于它具有特征吸收波长(301nm),因此可以用HPLC进行反应追踪。

基本文献

  • Carpino, A. L.; Han, G. Y. J. Am. Chem. Soc. 1970, 92, 5748. DOI: 10.1021/ja00722a043
  • Carpino, L. A.; Han, G. Y. J. Org. Chem. 1972, 37, 3404. DOI: 10.1021/jo00795a005
  • Carpino, L.; Han, G. J. Org. Chem. 1979, 44, 3739. DOI: 10.1021/jo01335a600
  • Fmoc-OSu: Sigler, G. F.; Fuller, W. D.; Chaturvedi, N. C.; Goodman, M.; Verlander, M. Biopolymers 1983, 22, 2157. doi:10.1002/bip.360221002
  • Fmoc-pfp:Schön, I.; Kisfaludy, L. Synthesis 1986, 303. DOI: 10.1055/s-1986-31591
  • Fmoc-DMT: Hioki, K.; Kinugasa, M.; Kishimoto, M.; Fujiwara, M.; Tani, S.; Kunishima, M. Synthesis 2006, 1931. DOI: 10.1055/s-2006-942389
  • Fmoc-Amox: Kumar, A.; Sharma, A.; Haimov, E.; El-Faham, A.; de la Torre, B. G.; Albericio, F. Org. Process Res. Dev. 2017, 21, 1533. DOI: 10.1021/acs.oprd.7b00199
Fmoc-SPPS
review
  • Carpino, L. A. Acc. Chem. Res. 1987, 20, 401. DOI: 10.1021/ar00143a003
  • Isidro-Llobet, A.; Álvarez, M.; Albericio, F. Chem. Rev. 2009, 109, 2455. DOI: 10.1021/cr800323s
  • Luna, O. F.; Gomez, J.; Cardenas, C.; Albericio, F.; Marshall, S. H.; Guzman, F.Molecules 2016, 21, 1542. doi:10.3390/molecules21111542

开发史

1970年代初由Louis A. Carpino开发

反应机理

保护

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作为反应试剂Fmoc-Cl是最常用的。保护反应也就是典型的酰氯+碱条件下的反应。对于氨基酸的保护等,使用无机碱的Schotten-Baumann条件也很常见。

脱保护

9位的proton酸性比较高,在温和的碱性条件下发生E1cB离去。由于作为副产物的二苯并富烯(DBF)可以再次充当亲电试剂并引起副反应,因此经常需要选择使用能够捕获它的碱。

由于这些原因,通常使用仲胺如哌啶作为脱保护的碱。溶媒はDMFが良く用いられる。3級アミンではほとんど切断されない。

Fmoc-Val-OH在DMF中进行脱保护的时候,使用不同的胺的脱保护反应速度如下图所示


cited by “Greene’s Protective Groups in Organic Synthesis”, 4th ed.

近年来,已经研究了用DBU和哌嗪代替哌啶的方法(RSC Adv. 2015, 5, 104417)。

反应实例

Calicheamicin γ1I全合成[1]:在多步骤中Fmoc体现出了两个的稳定性。

参考文献

  1. Nicolaou, K. C.; Groneberg, R. D.; Miyazaki, T.; Stylianides, N. A.; Schulze, T. J.; Stahl, W. J. Am. Chem. Soc. 1990, 112, 8193. DOI: 10.1021/ja00178a069

关联书籍(日亚价格)

Greene's Protective Groups in Organic Synthesis

Greene’s Protective Groups in Organic Synthesis

  • 著者Peter G. M. Wuts
  • 参考価格¥ 12,094日元
    価格¥ 11,813(2018/07/08 10:25時点)
  • 出版社John Wiley & Sons Inc

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LuWenjie

LuWenjie

京都大学药学博士,现某化学企业小职员,化学空间员工副代表,网页小编&翻译。

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