Preparative Method for Asymmetric Synthesis of ()-2-Amino-4,4,4-trifluorobutanoic Acid

Overview

Journal Molecules

Publisher MDPI

Specialty Biology

Date 2019 Dec 15

PMID 31835583

Citations 2

Authors

Jianlin Han

Ryosuke Takeda

Xinyi Liu

Hiroyuki Konno

Hidenori Abe

Takahiro Hiramatsu

Hiroki Moriwaki

Vadim A Soloshonok

Affiliations

Soon will be listed here.

Abstract

Enantiomerically pure derivatives of 2-amino-4,4,4-trifluorobutanoic acid are in great demand as bioisostere of leucine moiety in the drug design. Here, we disclose a method specifically developed for large-scale (>150 g) preparation of the target ()--Fmoc-2-amino-4,4,4-trifluorobutanoic acid. The method employs a recyclable chiral auxiliary to form the corresponding Ni(II) complex with glycine Schiff base, which is alkylated with CF-CH-I under basic conditions. The resultant alkylated Ni(II) complex is disassembled to reclaim the chiral auxiliary and 2-amino-4,4,4-trifluorobutanoic acid, which is in situ converted to the N-Fmoc derivative. The whole procedure was reproduced several times for consecutive preparation of over 300 g of the target ()--Fmoc-2-amino-4,4,4-trifluorobutanoic acid.

Citing Articles

Asymmetric Synthesis of Tailor-Made Amino Acids Using Chiral Ni(II) Complexes of Schiff Bases. An Update of the Recent Literature.

Zou Y, Han J, Saghyan A, Mkrtchyan A, Konno H, Moriwaki H Molecules. 2020; 25(12).

PMID: 32545684 PMC: 7356839. DOI: 10.3390/molecules25122739.

Special Issue: Development of Asymmetric Synthesis.

Chinchilla R Molecules. 2020; 25(6).

PMID: 32168826 PMC: 7143973. DOI: 10.3390/molecules25061266.

References

Belot V, Farran D, Jean M, Albalat M, Vanthuyne N, Roussel C . Steric Scale of Common Substituents from Rotational Barriers of N-(o-Substituted aryl)thiazoline-2-thione Atropisomers. J Org Chem. 2017; 82(19):10188-10200. DOI: 10.1021/acs.joc.7b01698. View

Soloshonok V, Ueki H . Design, synthesis, and characterization of binuclear Ni(II) complexes with inherent helical chirality. J Am Chem Soc. 2007; 129(9):2426-7. DOI: 10.1021/ja0671215. View

Hodgson D, Sanderson J . The synthesis of peptides and proteins containing non-natural amino acids. Chem Soc Rev. 2004; 33(7):422-30. DOI: 10.1039/b312953p. View

Takeda R, Kawamura A, Kawashima A, Sato T, Moriwaki H, Izawa K . Chemical dynamic kinetic resolution and S/R interconversion of unprotected α-amino acids. Angew Chem Int Ed Engl. 2014; 53(45):12214-7. DOI: 10.1002/anie.201407944. View

Lunazzi L, Mancinelli M, Mazzanti A, Lepri S, Ruzziconi R, Schlosser M . Rotational barriers of biphenyls having heavy heteroatoms as ortho-substituents: experimental and theoretical determination of steric effects. Org Biomol Chem. 2012; 10(9):1847-55. DOI: 10.1039/c1ob06688a. View

Metz A, Kozlowski M . Recent Advances in Asymmetric Catalytic Methods for the Formation of Acyclic α,α-Disubstituted α-Amino Acids. J Org Chem. 2014; 80(1):1-7. DOI: 10.1021/jo502408z. View

Zhu Y, Han J, Wang J, Shibata N, Sodeoka M, Soloshonok V . Modern Approaches for Asymmetric Construction of Carbon-Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs. Chem Rev. 2018; 118(7):3887-3964. PMC: 6497456. DOI: 10.1021/acs.chemrev.7b00778. View

Bouhlel A, Alyami W, Li A, Yuan L, Rich K, McConathy J . Effect of α-Methyl versus α-Hydrogen Substitution on Brain Availability and Tumor Imaging Properties of Heptanoic [F-18]Fluoroalkyl Amino Acids for Positron Emission Tomography (PET). J Med Chem. 2016; 59(7):3515-31. PMC: 4957663. DOI: 10.1021/acs.jmedchem.6b00189. View

Kiss L, Fulop F . Selective Synthesis of Fluorine-Containing Cyclic β-Amino Acid Scaffolds. Chem Rec. 2017; 18(3):266-281. DOI: 10.1002/tcr.201700038. View

10.

Yamada T, Okada T, Sakaguchi K, Ohfune Y, Ueki H, Soloshonok V . Efficient asymmetric synthesis of novel 4-substituted and configurationally stable analogues of thalidomide. Org Lett. 2006; 8(24):5625-8. DOI: 10.1021/ol0623668. View

11.

Oliver M, Gadais C, Garcia-Pindado J, Teixido M, Lensen N, Chaume G . Trifluoromethylated proline analogues as efficient tools to enhance the hydrophobicity and to promote passive diffusion transport of the l-prolyl-l-leucyl glycinamide (PLG) tripeptide. RSC Adv. 2022; 8(26):14597-14602. PMC: 9079923. DOI: 10.1039/c8ra02511h. View

12.

Takeda R, Kawamura A, Kawashima A, Sato T, Moriwaki H, Izawa K . Second-order asymmetric transformation and its application for the practical synthesis of α-amino acids. Org Biomol Chem. 2018; 16(27):4968-4972. DOI: 10.1039/c8ob00963e. View

13.

Han J, Kitagawa O, Wzorek A, Klika K, Soloshonok V . The self-disproportionation of enantiomers (SDE): a menace or an opportunity?. Chem Sci. 2018; 9(7):1718-1739. PMC: 5892310. DOI: 10.1039/c7sc05138g. View

14.

Bandak D, Babii O, Vasiuta R, Komarov I, Mykhailiuk P . Design and synthesis of novel 19F-amino acid: a promising 19F NMR label for peptide studies. Org Lett. 2014; 17(2):226-9. DOI: 10.1021/ol503300m. View

15.

Han J, Takeda R, Sato T, Moriwaki H, Abe H, Izawa K . Optical Resolution of Rimantadine. Molecules. 2019; 24(9). PMC: 6539882. DOI: 10.3390/molecules24091828. View

16.

Kondratov I, Logvinenko I, Tolmachova N, Morev R, Kliachyna M, Clausen F . Synthesis and physical chemical properties of 2-amino-4-(trifluoromethoxy)butanoic acid - a CFO-containing analogue of natural lipophilic amino acids. Org Biomol Chem. 2016; 15(3):672-679. DOI: 10.1039/c6ob02436j. View

17.

Sorochinsky A, Acena J, Moriwaki H, Sato T, Soloshonok V . Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 2: aldol, Mannich addition reactions, deracemization and (S) to (R) interconversion of α-amino acids. Amino Acids. 2013; 45(5):1017-33. DOI: 10.1007/s00726-013-1580-3. View

18.

Mei H, Han J, Fustero S, Medio-Simon M, Sedgwick D, Santi C . Fluorine-Containing Drugs Approved by the FDA in 2018. Chemistry. 2019; 25(51):11797-11819. DOI: 10.1002/chem.201901840. View

19.

Smits R, Cadicamo C, Burger K, Koksch B . Synthetic strategies to alpha-trifluoromethyl and alpha-difluoromethyl substituted alpha-amino acids. Chem Soc Rev. 2008; 37(8):1727-39. DOI: 10.1039/b800310f. View

20.

Acena J, Sorochinsky A, Soloshonok V . Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases. Part 3: Michael addition reactions and miscellaneous transformations. Amino Acids. 2014; 46(9):2047-73. DOI: 10.1007/s00726-014-1764-5. View