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Article Cite This: ACS Omega 2019, 4, 11844−11851
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Practical Method for Preparation of (S)‑2-Amino-5,5,5trifluoropentanoic Acid via Dynamic Kinetic Resolution Haibo Mei,† Jianlin Han,*,† Ryosuke Takeda,*,‡,§ Tsubasa Sakamoto,‡ Toshio Miwa,‡ Yutaka Minamitsuji,‡ Hiroki Moriwaki,*,‡ Hidenori Abe,‡ and Vadim A. Soloshonok*,§,∥ †
College of Chemical Engineering Nanjing Forestry University, Nanjing 210037, China Hamari Chemicals Ltd., 1-4-29 Kunijima, Higashi-Yodogawa-ku, Osaka 533-0024, Japan § Department of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel Lardizábal 3, San Sebastián 20018, Spain ∥ IKERBASQUEBasque Foundation for Science, María Díaz de Haro 3, Plaza Bizkaia, Bilbao 48013, Spain
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‡
S Supporting Information *
ABSTRACT: This work reports an operationally convenient ∼20 g scale synthesis of (S)-2-amino-5,5,5-trifluoropentanoic acid and its Fmoc-derivative via dynamic kinetic resolution of the corresponding racemate.
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trifluoropentanoic acid (1) (Figure 1), a fluorinated analogue naturally occurring in bacterial proteins norvaline (2),9 has
INTRODUCTION The development of more selective and potent pharmaceuticals is one of the most important missions of current organic chemistry. While the process of drug discovery is rather a complicated, multifaceted endeavor, careful structural analysis of the newly approved pharmaceuticals can reveal some essential trends in the successful formulations. For example, introduction of fluorinated groups into a drug candidate molecule usually leads to greater metabolic stability, activity, and overall favorable pharmacokinetics.1 Another general trend is the incorporation of tailor-made amino acid (AA)2 moieties allowing for more precise mimicking of peptide−receptor interactions as well as lowering the toxicity and undesirable side effects.3 Consequently, from the structural standpoint, fluorine-containing α-4 and β-AAs,5 featuring both essential traits, are considered to have pronounced pharmaceutical potential in the modern drug design.6 Chemistry of fluorinecontaining AAs and peptides, including synthesis and biological studies, published before 1994, is covered by a comprehensive monograph.7 Since then, this research field has grown tremendously, being updated by more specialized review articles4,5 and recent publications.6 Among various types of fluorinated tailor-made AAs, linear ω-CF3-AAs represent a family of structurally relatively simple, yet very useful compounds widely used in drug development and peptide research.8 In particular, (S)-2-amino-5,5,5© 2019 American Chemical Society
Figure 1. 2-Amino-5,5,5-trifluoropentanoic acid (1), its naturally occurring parent AA norvaline (2), and a γ-secretase inhibitor avagacestat (3).
been extensively used in the design of bioactive formulations10 and protein research.11 Quite remarkably, the residue of AA 1 played a key role in the development of avagacestat 3, a γsecretase inhibitor used in the treatment of Alzheimer disease.12 As a part of our current activity focused on the large-scale synthesis of a potential pharmaceutical agent, we needed a reliable access to multigram quantities of Received: May 26, 2019 Accepted: June 25, 2019 Published: July 9, 2019 11844
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In most of the applications, ligands 4 are first converted to glycine Ni(II) complexes of type 5, followed by the alkylation of the methylene moiety.22 A methodologically different approach involves a direct reaction of ligands 4 with racemic AAs, resulting in dynamic kinetic resolution, including (S)/ (R)-interconversion,23 and formation of major products 6 of (S,S) absolute configuration.24 Subsequently, application of (R)-configured ligands 4 gives rise to 6-(R,R) products, assuming a regular case of CIP priority. It is interesting to note that the dynamic kinetic resolution approach can also be successfully applied for β-AAs.25 Considering that both approaches can be used for the preparation of the target (S)2-amino-5,5,5-trifluoropentanoic acid (1) derivatives, we decided to examine each of them to find the most practical solution. Alkylation Approach. Drawing from our recent experience with the alkylation of glycine complex (S)-5 using CF3containing alkyl halides,6s−u we decided to use N,N-dimethylformamide (DMF) as a solvent and NaOH as a base for the reaction with 1,1,1-trifluoro-3-iodopropane, as presented in Scheme 2.
enantiomerically pure 2-amino-5,5,5-trifluoropentanoic acid 1 derivatives. A careful analysis of the literature data available for the preparation of the target AA 113 evidently indicated that the known approaches are not viable for the large-scale synthesis, prompting us to undertake an appropriate research project. For example, the most operationally convenient and scalable enzymatic resolution approach13e produces equal amount of unwanted enantiomer, which would be problematic for the large-scale preparation of only the target enantiomer. On the other hand, the purely chemical approaches for the asymmetric synthesis of AA 1,13d,f,j while efficient on a small scale, involve chromatographic purifications and strictly controlled reaction conditions, which would be quite problematic for a large-scale process. In this work, we examine two alternative approaches to synthesize AA 1, including alkylation of a chiral glycine equivalent vs. dynamic kinetic resolution (DKR) of the corresponding racemate. We disclose that the latter approach is significantly more practical, allowing convenient and reliable preparation of the target (S)-2-amino-5,5,5-trifluoropentanoic acid (1) derivatives on over 20 g scale. The obvious synthetic value of the procedure developed in the present work is that it does not require any special conditions or chromatographic purifications and can be recommended as a method of choice for low-cost, large-scale synthesis.
Scheme 2. Alkylation of Chiral Glycine Equivalent (S)-5
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RESULTS AND DISCUSSION Consistent with our continuous interest in asymmetric synthesis of various types of tailor-made fluorine-, 14 phosphorus-containing,15 sterically constrained16 AAs, as well as self-disproportionation of enantiomers17 of AA derivatives, we are actively developing chemistry of Ni(II) complexes derived from AA Schiff bases3e,18 as a general method for the preparation of tailor-made AAs. Using the modular approach for designing chiral tridentate ligands, 19 recently, we introduced strategically tri-chlorosubstituted ligands (R)- and (S)-4 (Scheme 1)20 possessing the optimized stereocontrolling properties.21 Scheme 1(A) shows the preparation of nucleophilic glycine equivalent (S,S)-6. Scheme 1(B) gives the alkylation of glycine complex (S)-5. Scheme 1(C) shows the dynamic kinetic resolution of unprotected AAs. Scheme 1. Applications of Tridentate Ligand (S)-4 for General Asymmetric Synthesis of α-AAs Analysis of the reaction mixture by thin-layer chromatography and high-performance liquid chromatography revealed the presence of several byproducts including minor diastereomer (S)(2R)-7, bis-alkylated complex (S)-8, and 4-phenylquinazoline (S)-9, typical for this reactions.6s,t As was previously shown,26 compound (S)-9 is the end product of the reaction of complexes of types 5 and 7 with atmospheric oxygen, leading to the cleavage of the N−C bond, followed by the cyclization involving the proline carbonyl. It should be noted that first attempts to use the conditions optimized for alkylations of (S)-5 with CF3−CH2−I and CF3−(CH2)3−I6s,t were rather unsuccessful. Most likely, the application of a base in homogeneous form like NaOMe, solutions, or ground to powder NaOH led to noticeable decomposition of the alkylation reagent due to the favorable formation of CF3− CHCH2. Also, in this case, the application of commercialgrade DMF gave unexpectedly higher amounts of oxidation 11845
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5,5,5-trifluoropentanoic acid 11 in methanol in the presence of a base and source of Ni(II) ions to furnish the target product (S,S)-7. After a series of reactions conducted to optimize the reaction conditions, it was determined that K2CO3 and NiCl2 were the best-performing base and Ni(II) source, respectively. Of particular importance was the optimization of stoichiometric ratios between all of the reagents. Thus, considering the fact that ligand (S)-4 is more expensive than racemate 11, we used the latter in excess, calculating the chemical yield based on ligand (S)-4. The best yield of the product (S,S)-7 (97.0%) was obtained with the application of 1.4 equiv excess of rac-11 and NiCl2, using 7 equiv of the base. Relatively large excess of K2CO3 (7 equiv) was needed due to the necessity to neutralize 2 equiv of HCl, transforming both starting ligand (S)-4 and AA rac-11 to a free base and zwitterion, respectively. Most importantly, under these conditions, product (S,S)-7 was obtained in a virtually diastereomerically pure form (99.5% de). This aspect of the developed process is of utmost synthetic value, as no other additional purification is required to proceed to the next disassembly stage (vide infra). Furthermore, the isolation of (S,S)-7 was achieved simply by filtration of the precipitate formed after pouring of the reaction mixture into aqueous acetic acid. Moreover, we also examined the reproducibility of this method for small- as well as largerscale reactions. For example, using 16.6 g of ligand (S)-4, we prepared 38.7 g of (S,S)-7 (97% yield, 99.5% de). The next synthetic step, the disassembly of this prepared product (S,S)-7, is presented in Scheme 5.
product (S)-9. Nevertheless, we were able to obtain the undesired reactivity and byproduct formation by using NaOH beads and highly controlled conditions such as dry and deoxygenated DMF. In fact, on the 1 g scale, under these conditions, we obtained rather good chemical yield and diastereoselectivity. Thus, the major diastereomer (S,S)-7 was isolated with 98.4% yield and of 84.0% de. Attempts to scale up this procedure were much successful, however. Likely, a problematic homogenization of the reaction mixture, increased decomposition of the alkylating reagent, and difficulties associated with handling larger amounts of solvent and the reagents resulted in deteriorated chemical yields and stereochemical outcome. Dynamic Kinetic Resolution Approach. In general, dynamic kinetic resolution (DKR) of unprotected α- and βAAs using ligands of type (S)-4 is almost ideal methodology for practical large-scale preparation of enantiomerically pure tailor-made AAs.23−25 Nevertheless, one particular limitation of this approach is the availability of starting racemic AA. In our case, the racemic 2-amino-5,5,5-trifluoropentanoic acid is quite inexpensive and commercially available as N-acetyl derivative 10 (Scheme 3). Scheme 3. Preparation of Racemic 2-Amino-5,5,5trifluoropentanoic Acid Hydrochloride 11
Scheme 5. Disassembly of Diastereomer (S,S)-7; Isolation of Free Zwitterionic AA (S)-1; and Recycling of Ligand (S)4
After a series of experiments, using various conditions to perform a cleavage of the amide bond in 10, we finally chose 6 N aqueous hydrochloric acid. Thus, heating of amide 10 with 6 N HCl at 100 °C for 4 h led to the desired hydrolysis with quantitative chemical yield. Purification of hydrochloric salt 11 was achieved simply by washing of the crude product and filtration of chemically pure compound 11, isolated with 88.8% yield. In contrast to the alkylation procedure, DKR is usually conducted in an alcohol solvent and the process is not complicated by oxidative reactions, leading to the byproducts of type (S)-9. Accordingly, DKR can be conducted under convenient, not-so-strictly controlled conditions, even in open air, showing a great potential for large-scale synthesis.23−25 As presented in Scheme 4, tridentate ligand (S)-4, used as a hydrochloric salt, was reacted with hydrochloride of 2-amino-
As stated above, product (S,S)-7 obtained by the DKR procedure, without any additional purification, was subjected to the disassembly procedure under the action of 3 N HCl in
Scheme 4. Dynamic Kinetic Resolution of Racemic Unprotected 2-Amino-5,5,5-trifluoropentanoic Acid Hydrochloride 11
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methanol (50 °C for 5 h). Upon disappearance of a typical red−orange color of the Ni(II) complex (S,S)-7, the reaction mixture was allowed to gradually cool down to ambient temperature, resulting in the formation of a precipitate of the hydrochloric salt of ligand (S)-4. The precipitate was filtered off, allowing for a convenient recycling (∼90%) of the stereochemically intact chiral ligand (S)-4, which can be reused for the preparation of new batches of AA (S)-1 or other synthetic applications. The target AA (S)-1 was isolated with over 98% yield using a rather standard procedure with cationexchange resin and 9% ammonium hydroxide as an eluent. While the isolation of free zwitterionic AA (S)-1 was conceptually important to demonstrate the conventional preparative value of this method, for our development purposes, we needed an access to AA (S)-1 in a form suitable for peptide synthesis. To this goal, we performed a modified disassembly procedure as presented in Scheme 6.
recycling of the chiral ligand, bodes well for the widespread application of this method.
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EXPERIMENTAL SECTION Procedure for Alkylation of Chiral Glycine Equivalent (S)-5. The Ni−Glycine complex (S)-5 (1.0 g, 1.66 mmol) and 1,1,1-trifluoro-3-iodopropane (0.21 mL, 1.83 mmol) were stirred in deoxygenated N,N-dimethyl-formamide (DMF) (10 mL) at room temperature (rt) under nitrogen. Then, NaOH (beads) (0.080 g, 2.00 mmol) was added into the above mixture. The resulting solution was stirred at room temperature for 2 h and then poured into water (10 mL) and EtOAc (10 mL) at the same temperature. The mixture was separated, and the aqueous layer was extracted with EtOAc (2 × 10 mL). The combined organic layer was washed with brine, dried over Na2SO4, and then evaporated to afford (S,S)-7 (1.14 g, 98.4, 84.0% de). Preparation of Racemic 2-Amino-5,5,5-trifluoropentanoic Acid Hydrochloride 11. The mixture of Ac-AA 10 (50.4 g, 236 mmol) and 6 N hydrochloric acid aq. (202 mL, 1210 mmol) was heated at 100 °C for 4 h. After the reaction was complete, the reaction mixture was cooled, concentrated, and dried in vacuo at 50 °C for 3 h, in which the compound was loosened for good dryness, to give 50 g of a crude. The crude was ground to a powder as fine as possible and then washed by stirring in acetonitrile (250 mL) for 30 min. The resulting sticky suspension was filtered, washed with acetonitrile (100 mL), and dried in vacuo at 50 °C overnight to afford the AA HCl salt 11 (43.6 g, 88.8%). 11: 1H NMR (200 MHz, D2O): δ 4.12 (t, J = 6.2 Hz, 1H), 2.30−2.60 (m, 2H), 2.05−2.30 (m, 2H). Procedure for the Dynamic Kinetic Resolution of Racemic Unprotected 2-Amino-5,5,5-trifluoropentanoic Acid Hydrochloride 11. To a mixture of AA HCl salt 11 (16.6 g, 80.1 mmol), ligand (S)-4 (30.0 g, 57.2 mmol), nickel(II) chloride anhydrous (10.4 g, 80.1 mmol), and degassed methanol (900 mL) was added potassium carbonate (55.4 g, 401 mmol). The reaction mixture was stirred at 50 °C for 2.5 h. After the ligand (S)-3 was consumed, the reaction mixture was gradually cooled to around 30 °C and then to 0 °C. The cooled mixture was poured into a cooled acetic acid (45.8 mL, 801 mmol)/distilled water (1800 mL) solution at 0 °C for 30 min to quench and give a precipitate. After stirring for 30 min at 0 °C, the precipitate was filtrated, washed with distilled water, and dried in vacuo at 50 °C overnight to afford the diastereomeric mixture of the Ni(II) complex (S,S)-7 (38.7 g, 97.0, 99.5% de). (S,S)-7: 1H NMR (400 MHz, CDCl3): δ = 8.90 (d, J = 2.0 Hz, 1H), 8.06 (d, J = 9.2 Hz, 1H), 7.76 (dd, J = 2.0, 8.1 Hz, 1H), 7.48−7.62 (m, 3H), 7.38 (d, J = 8.1 Hz, 1H), 7.27−7.31 (m, 1H), 7.14 (dd, J = 2.5, 9.2 Hz, 1H), 6.90 (d, J = 7.4 Hz, 1H), 6.60 (d, J = 2.6 Hz, 1H), 4.33 (d, J = 12.5 Hz, 1H), 3.83 (dd, J = 3.6, 9.9 Hz, 1H), 3.51−3.57 (m, 2H), 3.39 (dd, J = 5.7, 11.1 Hz, 1H), 3.23 (d, J = 12.5 Hz, 1H), 2.55−2.76 (m, 3H), 2.22−2.47 (m, 2H), 1.95−2.17 (m, 2H), 1.76−1.89 (m, 1H). 13C NMR (100 MHz, CDCl3): δ = 23.9, 28.2 (J = 3.0 Hz, d), 30.1 (J = 29.0 Hz, q), 30.8, 58.4, 63.1, 68.8, 71.2, 124.3, 125.9, 126.3 (J = 275.0 Hz, q), 126.9, 127.0, 127.1, 129.5, 129.5, 129.9, 130.5, 131.1, 132.2, 132.4, 132.7, 133.4, 133.6, 134.8, 140.6, 171.0, 177.9, 180.0. 19F NMR (376 MHz, CDCl3): δ = −67.6 (CF3). IR (KBr): ν = 2962, 2867, 1678, 1647, 1534, 1464, 1397, 1250, 1166, 1077, 822 cm−1. MS (ESI): m/z = 718.0 [M + Na]+.
Scheme 6. Disassembly of Diastereomer (S,S)-7; Isolation of Fmoc-AA (S)-12; and Recycling of Ligand (S)-4
First, instead of methanol, we used dimethoxyethane (DME), which improved the solubility of complex (S,S)-7, leading to overall smaller volumes of solvents and a bit greater disassembly rate. The recycling of chiral ligand (S)-4 was achieved by filtration, quite similar to the procedure discussed above (Scheme 5). The solution of AA (S)-1 with NiCl2 was first treated with ethylenediaminetetraacetic acid (EDTA) to chelate the Ni(II) ions, followed by the standard reaction using the Fmoc-OSu reagent under basic conditions. The target Fmoc-derivative (S)-12 was isolated with excellent chemical yield (93.3%) and acceptable enantiomeric purity (98.2% ee). Finally, it should be noted that the described DKR procedures were also applied for the preparation of (R)-2amino-5,5,5-trifluoropentanoic acid 1 and its Fmoc-derivative 12 using (R)-configured chiral ligand 4.
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CONCLUSIONS In this work, we examined two alternative approaches for the preparation of (S)-2-amino-5,5,5-trifluoropentanoic acid and its Fmoc-derivative. We found that while the alkylation procedure can be successfully performed on an ∼1 g scale, the dynamic kinetic resolution is generally a more practical solution for scaled up (∼20 g) synthesis. The operational convenience of all chemical transformations coupled with excellent chemical yields and diastereoselectivity, as well as the 11847
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Procedure for Disassembly of Diastereomer (S,S)-7; Isolation of Free Zwitterionic AA (S)-1; and Recycling of Ligand (S)-4. To a suspension of the Ni(II) complex (S,S)-7 (33.6 g, 48.2 mmol) in methanol (336 mL) was added 3 N hydrochloric acid aq. (80 mL, 240 mmol), and the whole mixture was heated at 50 °C for 5 h. After the completion of the reaction, the mixture was cooled to ambient temperature. The resulting precipitate was collected by filtration (recovered ligand (S)-4), and the filtrate was concentrated. CH2Cl2 (250 mL) and H2O (200 mL) were added to the residue, and then the mixture was separated. The aqueous layer was evaporated in vacuo to the residue, which was dissolved in minimum amount of 9% ammonium hydroxide and loaded onto a cationexchange resin column using DIAION SK-1B (Mitsubishi Chemical Co., 440 mL). The column was first washed with deionized water until neutral, followed by 9% ammonium hydroxide to elute the desired amino acid. The aqueous solution obtained was evaporated to afford AA (S)-1 (8.34 g, quant., 99.2% ee). (S)-1: 1H NMR (200 MHz, CD3OD): δ = 3.60 (t, J = 6.1 Hz, 1H), 2.16−2.57 (m, 2H), 1.96−2.16 (m, 2H). Procedure for Disassembly of Diastereomer (S,S)-7; Isolation of Fmoc-AA (S)-12; and Recycling of Ligand (S)-4. To a suspension of the Ni(II) complex (S,S)-7 (38.5 g, 55.2 mmol) in 1,2-dimetoxyethane (193 mL) was added 3 N hydrochloric acid aq. (92.0 mL, 276 mmol), and the whole mixture was heated at 50 °C for 3 h. After the completion of the reaction, the mixture was cooled to ambient temperature. The resulting precipitate was collected by filtration (1st recovered ligand (S)-3), and the filtrate was concentrated to remove 1,2-dimetoxyethane and give a white solid in a green solution. The suspension was stirred at rt for 2 h and filtered to separate the solid (2nd recovered ligand (S)-4). The filtrate was concentrated as much as possible to give AA (S)-1 as a green muddy solid (38.8 g, theoretically 9.44 g of amino acid). To the solid were added distilled water (47 mL), ethylenediaminetetraacetic acid (EDTA) disodium salt dihydrate (20.5 g, 55.2 mmol), and acetonitrile (27 mL), and the whole mixture was stirred at rt for 30 min. After cooling to 0 °C, the mixture was basified with sodium carbonate to pH over 8. After stirring at 0 °C for 10 min, to this heterogeneous solution was added a suspension of N-(9fluorenylmethoxycarbonyloxy)succinimide (Fmoc-OSu) (18.6 g, 55.2 mmol) in acetonitrile (20 mL) and stirred at rt for 4 h with the pH over 8 by addition of sodium carbonate. After evaporation of the organic solvent, to the aqueous residue was added ethyl acetate (47 mL). The mixture was acidified with 6 N HCl to pH 1 to give a precipitate that dissolved with another ethyl acetate (47 mL). After the separation of an organic layer and an aqueous layer, the aqueous layer was extracted with ethyl acetate (x3). The combined organic layers were washed with water and brain and dried over sodium sulfate. The organic solution was concentrated to afford crude Fmoc-AA (S)-12. The crude solid was recrystallized from ethyl acetate/ heptane (1:30, 1350 mL) and dried in vacuo at 50 °C to afford Fmoc-AA (S)-12 (20.2 g, 93.3, 98.2% ee). 12: 1H NMR (400 MHz, CD3OD): δ 7.78 (2H), 7.67 (2H), 7.36 (2H), 7.29 (2H), 4.36 (2H), 4.19 (2H), 2.35−1.82 (m, 4H). 19F NMR (376 MHz, CDCl3): δ = −66.86 (CF3). MS (ESI): m/z = 416 [M + Na]+.
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ASSOCIATED CONTENT
* Supporting Information S
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsomega.9b01537. Full spectroscopic data and copies of 1H NMR and 13C NMR spectra. General procedure for the alkylation reaction of 5. Preparation of racemic 2-amino-5,5,5trifluoropentanoic acid hydrochloride 11. Dynamic kinetic resolution of racemic 11. Disassembly of diastereomer (S,S)-7 and ion-exchange column isolation. Disassembly of diastereomer (S,S)-7 and the formation of Fmoc-derivative (PDF)
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AUTHOR INFORMATION
Corresponding Authors
*E-mail: *E-mail: *E-mail: *E-mail:
[email protected] (J.H.).
[email protected] (R.T.).
[email protected] (H.M.).
[email protected] (V.A.S.).
ORCID
Jianlin Han: 0000-0002-3817-0764 Ryosuke Takeda: 0000-0003-4502-8368 Vadim A. Soloshonok: 0000-0003-0681-4526 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS We gratefully acknowledge the financial support from the National Natural Science Foundation of China (Nos. 21761132021 and 21606133), the Natural Scientific Foundation of Jiangsu Province, P. R. China (No. Bk20160922), and IKERBASQUE, Basque Foundation for Science.
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REFERENCES
(1) (a) Wang, J.; Sánchez-Roselló, M.; Aceña, J. L.; del Pozo, C.; Sorochinsky, A. E.; Fustero, S.; Soloshonok, V. A.; Liu, H. Fluorine in Pharmaceutical Industry: Fluorine-Containing Drugs Introduced to the Market in the Last Decade (2001−2011). Chem. Rev. 2014, 114, 2432−2506. (b) Zhu, W.; Wang, J.; Wang, S.; Gu, Z.; Aceña, J. L.; Izawa, K.; Liu, H.; Soloshonok, V. A. Recent advances in the trifluoromethylation methodology and new CF3-containing drugs. J. Fluorine Chem. 2014, 167, 37−54. (c) Zhou, Y.; Wang, J.; Gu, Z.; Wang, S.; Zhu, W.; Aceña, J. L.; Soloshonok, V. A.; Izawa, K.; Liu, H. Next Generation of Fluorine-Containing Pharmaceuticals, Compounds Currently in Phase II−III Clinical Trials of Major Pharmaceutical Companies: New Structural Trends and Therapeutic Areas. Chem. Rev. 2016, 116, 422−518. (d) Zhu, Y.; Han, J. L.; Wang, J.; Shibata, N.; Sodeoka, M.; Soloshonok, V. A.; Coelho, J. A. S.; Toste, F. D. Modern Approaches for Asymmetric Construction of Carbon−Fluorine Quaternary Stereogenic Centers: Synthetic Challenges and Pharmaceutical Needs. Chem. Rev. 2018, 118, 3887−3964. (e) Mei, H.; Han, J.; Fustero, S.; Medio-Simon, M.; Sedgwick, D. M.; Santi, C.; Ruzziconi, R.; Soloshonok, V. A. Fluorine-Containing Drugs Approved by the FDA in 2018. Chem. - Eur. J. 2019, No. 840. (2) For the definition of tailor-made amino acids, see: Soloshonok, V. A.; Cai, C.; Hruby, V. J.; Meervelt, L. V. Asymmetric Synthesis of Novel Highly Sterically Constrained (2S,3S)-3-Methyl-3-Trifluoromethyl- and (2S,3S,4R)-3-Trifluoromethyl-4-Methylpyroglutamic Acids. Tetrahedron 1999, 55, 12045−12058. (3) (a) Henninot, A.; Collins, J. C.; Nuss, J. M. The current state of peptide drug discovery: back to the future? J. Med. Chem. 2018, 61, 1382−1414. (b) Blaskovich, M. A. T. Unusual amino acids in medicinal chemistry. J. Med. Chem. 2016, 59, 10807−10836. (c) Ma, 11848
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bromodifluoroacetate to α,β-unsaturated α-amino acid derivatives. J. Fluorine Chem. 2018, 211, 100−108. (d) Oliver, M.; Gadais, C.; Garcia-Pindado, J.; Teixido, M.; Lensen, N.; Chaume, G.; Brigaud, T. 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. 2018, 8, 14597−14602. (e) Makki, M. S. T.; Abdel-Rahman; Reda, M.; Alharbi, A. S. Synthetic Approach for Novel Fluorine Substituted αAminophosphonic Acids Containing 1,2,4-Triazin-5-One Moiety as Antioxidant Agents. Int. J. Org. Chem. 2018, 8, 1−15. (f) Zhao, J. B.; Ren, X.; Zheng, B. Q.; Ji, J.; Qiu, Z. B.; Li, Y. Tetrahedron Lett. 2018, 59, 2091−2094. (g) Bucci, R.; Das, P.; Iannuzzi, F.; Feligioni, M.; Gandolfi, R.; Gelmi, M. L.; Reches, M.; Pellegrino, S. Self-assembly of an amphipathic ααβ-tripeptide into cationic spherical particles for intracellular delivery. Org. Biomol. Chem. 2017, 15, 6773−6779. (h) Betts, H. M.; Milicevic Sephton, S.; Tong, C.; Awais, R. O.; Hill, P. J.; Perkins, A. C.; Aigbirhio, F. I. Synthesis, in vitro evaluation, and radiolabeling of fluorinated puromycin analogues: Potential candidates for PET imaging of protein synthesis. J. Med. Chem. 2016, 59, 9422−9430. (i) 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 [F18]Fluoroalkyl Amino Acids for Positron Emission Tomography (PET). J. Med. Chem. 2016, 59, 3515−3531. (j) Ayoup, M. S.; Cordes, D. B.; Slawin, A. M. Z.; O’Hagan, D. Fluorine containing amino acids: synthesis and peptide coupling of amino acids containing the all-cis tetrafluorocyclohexyl motif. Org. Biomol. Chem. 2015, 13, 5621−5624. (k) Bandak, D.; Babii, O.; Vasiuta, R.; Komarov, I. V.; Mykhailiuk, P. K. Design and synthesis of novel 19F-amino acid: A promising 19F NMR label for peptide studies. Org. Lett. 2015, 17, 226−229. (l) Usuki, Y.; Wakamatsu, Y.; Yabu, M.; Iio, H. A New Access to Fluorine-containing Asparagine and Glutamine Analogues via Pd-catalyzed Formate Reduction. Asian J. Org. Chem. 2014, 3, 1270−1272. (m) Tkachenko, A. N.; Mykhailiuk, P. K.; Radchenko, D. S.; Babii, O.; Afonin, S.; Ulrich, A. S.; Komarov, I. V. Design and Synthesis of a Monofluoro-Substituted Aromatic Amino Acid as a Conformationally Restricted 19F NMR Label for Membrane-Bound Peptides. Eur. J. Org. Chem. 2014, 2014, 3584−3591. (n) Shibata, N.; Nishimine, T.; Shibata, N.; Tokunaga, E.; Kawada, K.; Kagawa, T.; Sorochinsky, A. E.; Soloshonok, V. A. Organic base-catalyzed stereodivergent synthesis of (R)- and (S)-3-amino-4,4,4-trifluorobutanoic acids. Chem. Commun. 2012, 48, 4124−4126. (o) Shibata, N.; Nishimine, T.; Shibata, N.; Tokunaga, E.; Kawada, K.; Kagawa, T.; Aceña, J. L.; Sorochinsky, A. E.; Soloshonok, V. A. Asymmetric Mannich reaction between (S)-N-(tertbutanesulfinyl)-3,3,3-trifluoroacetaldimine and malonic acid derivatives. Stereodivergent synthesis of (R)- and (S)-3-amino-4,4,4-trifluorobutanoic acids. Org. Biomol. Chem. 2014, 12, 1454−1462. (p) Kiss, L.; Fueloep, F. Selective Synthesis of Fluorine-Containing Cyclic β-Amino Acid Scaffolds. Chem. Rec. 2018, 18, 266−281. (r) Milcent, T.; Hao, J.; Kawada, K.; Soloshonok, V. A.; Ongeri, S.; Crousse, B. Highly Stereoselective azaBaylis−Hillman Reactions of CF3-Sulfinylimines: Straightforward Access to α-Methylene β-CF3 β-Amino Acids. Eur. J. Org. Chem. 2014, 2014, 3072−3075. (q) Drouet, F.; Noisier, A. F. M.; Harris, C. S.; Furkert, D. P.; Brimble, M. A. A Convenient Method for the Asymmetric Synthesis of Fluorinated α-Amino Acids from Alcohols. Eur. J. Org. Chem. 2014, 2014, 1195−1201. (s) Mei, H.; Hiramatsu, T.; Takeda, R.; Moriwaki, H.; Abe, H.; Han, J.; Soloshonok, V. A. Expedient Asymmetric Synthesis of (S)-2-Amino-4,4,4-trifluorobutanoic Acid via Alkylation of Chiral Nucleophilic Glycine Equivalent. Org. Process Res. Dev. 2019, 23, 629−634. (t) Mei, H.; Yin, Z.; Miwa, T.; Moriwaki, H.; Abe, H.; Han, J.; Soloshonok, V. A. Convenient Asymmetric Synthesis of Fmoc-(S)-6,6,6-trifluoro-Norleucine. Symmetry 2019, 11, 578. (u) Yin, Z.; Moriwaki, H.; Abe, H.; Miwa, T.; Han, J.; Soloshonok, V. A. Large-Scale Asymmetric Synthesis of Fmoc-(S)-2-Amino-6,6,6-Trifluorohexanoic Acid. ChemistryOpen 2019, 8, 701−704. (7) Fluorine-Containing Amino Acids: Synthesis and Properties, Kukhar, V. P., Soloshonok, V. A., Eds., John Wiley & Sons Ltd., 1994.
J. S. Unnatural amino acids in drug discovery. Chim. Oggi-Chem. Today 2003, 21, 65−68. (d) Hodgson, D. R. W.; Sanderson, J. M. The synthesis of peptides and proteins containing non-natural amino acids. Chem. Soc. Rev. 2004, 33, 422−430. (e) Sato, T.; Izawa, K.; Aceña, J. L.; Liu, H.; Soloshonok, V. A. Tailor-Made α-Amino Acids in the Pharmaceutical Industry: Synthetic Approaches to (1R, 2S)-1Amino-2-vinylcyclopropane-1-carboxylic Acid (Vinyl-ACCA). Eur. J. Org. Chem. 2016, 2757−2774. (f) Sorochinsky, A. E.; Aceña, J. L.; Moriwaki, H.; Sato, T.; Soloshonok, V. A. Asymmetric synthesis of αamino acids via homologation of Ni (II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations. Amino Acids 2013, 45, 691−718. (g) . Asymmetric Synthesis and Application of alpha-Amino Acids; Soloshonok, V. A., Izawa, K., Eds.; ACS Symposium Series 1009; Oxford University Press, 2009. (h) Soloshonok, V. A.; Sorochinsky, A. E. Practical Methods for the Synthesis of Symmetrically α,αDisubstituted-α-Amino Acids. Synthesis 2010, 2319−2344. (i) Wang, S.; Wang, Y.; Wang, J.; Sato, T.; Izawa, K.; Soloshonok, V. A.; Liu, H. The second-generation of highly potent hepatitis C virus (HCV) NS3/4A protease inhibitors: Evolutionary design based on tailor-made amino acids, synthesis and major features of bioactivity. Curr. Pharm. Des. 2017, 23, 4493−4554. (4) Recent reviews: (a) Smits, R.; Cadicamo, C. D.; Burger, K.; Koksch, B. Synthetic strategies to α-trifluoromethyl and αdifluoromethyl substituted α-amino acids. Chem. Soc. Rev. 2008, 37, 1727−1739. (b) Kukhar, V. P.; Sorochinsky, A. E.; Soloshonok, V. A. Practical synthesis of fluorine containing α- and β-amino acids: recipes from Kiev, Ukraine. Future Med. Chem. 2009, 1, 793−819. (c) Sorochinsky, A. E.; Soloshonok, V. A. Asymmetric synthesis of fluorine-containing amines, amino alcohols, α- and β-amino acids mediated by chiral sulfinyl group. J. Fluorine Chem. 2010, 131, 127− 139. (d) Tarui, A.; Sato, K.; Omote, M.; Kumadaki, I.; Ando, A. Stereoselective synthesis of α-fluorinated amino acid derivatives. Adv. Synth. Catal. 2010, 352, 2733−2744. (e) Czekelius, C.; Tzschucke, C. C. Synthesis of halogenated carboxylic acids and amino acids. Synthesis 2010, 543−566. (f) Qiu, X.-L.; Qing, F.-L. Recent advances in the synthesis of fluorinated amino acids. Eur. J. Org. Chem. 2011, 3261−3278. (g) Turcheniuk, K. V.; Kukhar, V. P.; Roeschenthaler, G.-V.; Acena, J. L.; Soloshonok, V. A.; Sorochinsky, A. E. Recent advances in the synthesis of fluorinated aminophosphonates and aminophosphonic acids. RSC Adv. 2013, 3, 6693−6716. (h) Aceña, J. L.; Sorochinsky, A. E.; Soloshonok, V. A. Recent Advances in the Asymmetric Synthesis of α-(Trifluoromethyl)-Containing α-Amino Acids. Synthesis 2012, 44, 1591−1602. (i) Aceña, J. L.; Sorochinsky, A. E.; Moriwaki, H.; Sato, T.; Soloshonok, V. A. Synthesis of fluorine containing α-amino acids in enantiomerically pure form via homologation of Ni(II) complexes of glycine and alanine Schiff bases. J. Fluorine Chem. 2013, 155, 21−38. (5) (a) Mikami, K.; Fustero, S.; Sánchez-Roselló, M.; Aceña, J. L.; Soloshonok, V. A.; Sorochinsky, A. E. Synthesis of fluorinated AQ3: Please provide a DOI number for ref 5a or indicate if one doesn’t exist.beta-amino acids. Synthesis 2011, 2011, 3045−3079. (b) Han, J.; Sorochinsky, A. E.; Ono, T.; Soloshonok, V. A. Biomimetic Transamination-a Metal-Free Alternative to the Reductive Amination. Application for Generalized Preparation of Fluorine-Containing Amines and Amino Acids. Curr. Org. Synth. 2011, 8, 281−294. (c) Luis Acena, J.; Simon-Fuentes, A.; Santos, F. Recent Developments in the Synthesis of Fluorinated β-Amino Acids. Curr. Org. Chem. 2010, 14, 928−949. (6) For recent publications, see: (a) Hao, J.; Milcent, T.; Retailleau, P.; Soloshonok, V. A.; Ongeri, S.; Crousse, B. Asymmetric Synthesis of Cyclic Fluorinated Amino Acids. Eur. J. Org. Chem. 2018, 3688− 3692. (b) Peng, Y. Y.; Liu, P.; Liu, Z. J.; Liu, J. T.; Mao, H. F.; Yao, Y. L. Regio- and diastereoselective Reformatsky reaction of chiral fluoroalkyl α,β-unsaturated N-tert-butanesulfinyl ketimines: Efficient asymmetric synthesis of β-fluoroalkyl β-vinyl β-amino esters. Tetrahedron 2018, 74, 3074−3080. (c) Kondratov, I. S.; Bugera, M. Y.; Tolmachova, N. A.; Daniliuc, C. G.; Haufe, G. Straightforward synthesis of fluorinated amino acids by Michael addition of ethyl 11849
DOI: 10.1021/acsomega.9b01537 ACS Omega 2019, 4, 11844−11851
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55, 14595−14599. (b) Kubyshkin, V.; Afonin, S.; Kara, S.; Budisa, N.; Mykhailiuk, P. K.; Ulrich, A. S. γ-(S)-Trifluoromethyl proline: evaluation as a structural substitute of proline for solid state 19FNMR peptide studies. Org. Biomol. Chem. 2015, 13, 3171−3181. (c) Tkachenko, A. N.; Mykhailiuk, P. K.; Afonin, S.; Radchenko, D. S.; Kubyshkin, V. S.; Ulrich, A. S.; Komarov, I. V. A 19F NMR Label To Substitute Polar Amino Acids in Peptides: A CF3-Substituted Analogue of Serine and Threonine. Angew. Chem., Int. Ed. 2013, 52, 1486−1489. (d) Mykhailiuk, P. K.; Afonin, S.; Palamarchuk, G. V.; Shishkin, O. V.; Ulrich, A. S.; Komarov, I. V. Synthesis of trifluoromethyl-substituted proline analogues as 19F NMR labels for peptides in the polyproline II conformation. Angew. Chem., Int. Ed. 2008, 47, 5765−5767. (12) (a) Maharvi, G. M.; Fauq, A. H. A synthesis of the γ-secretase inhibitor BMS-708163. Tetrahedron Lett. 2010, 51, 6542−6544. (b) Crump, C. J.; Castro, S. V.; Wang, F.; Pozdnyakov, N.; Ballard, T. E.; Sisodia, S. S.; Bales, K. R.; Johnson, D. S.; Li, Y. M. BMS-708,163 targets presenilin and lacks notch-sparing activity. Biochemistry 2012, 51, 7209−7211. (c) Hopkins, C. R. ACS Chemical Neuroscience Molecule Spotlight on BMS-708163. ACS Chem. Neurosci. 2012, 3, 149−150. (d) Dockens, R.; Wang, J. S.; Castaneda, L.; Sverdlov, O.; Huang, S. P.; Slemmon, R.; Gu, H.; Wong, O.; Li, H.; Berman, R. M.; Smith, C.; Albright, C. F.; Tong, G. A placebo-controlled, multiple ascending dose study to evaluate the safety, pharmacokinetics and pharmacodynamics of avagacestat (BMS-708163) in healthy young and elderly subjects. Clin. Pharmacokinet. 2012, 51, 681−693. (13) (a) Babb, R. M.; Bollinger, F. W. ω,ω,ω-Trifluoroamine acids. J. Org. Chem. 1970, 35, 1438−1440. (b) Ojima, I.; Kato, K.; Nakahashi, K.; Fuchikami, T.; Fujita, M. New and effective routes to fluoro analogs of aliphatic and aromatic amino acids. J. Org. Chem. 1989, 54, 4511−4522. (c) Urata, H.; Ishii, Y.; Fuchikami, T. Palladium-catalyzed double carbonylation of alkyl iodides bearing perfluoroalkyl group. Tetrahedron Lett. 1989, 30, 4407−4410. (d) Chen, Q.; Qiu, X. L.; Qing, F. L. Nucleophilic addition of 3,3,3-trifluoropropynyllithium to D-glyceraldimine: concise synthesis of both enantiomers of 5,5,5-trifluoronorvaline. J. Fluorine Chem. 2007, 128, 1182−1186. (e) Hanson, R. L.; Johnston, R. M.; Goldberg, S. L.; Parker, W. L.; Goswami, A. Enzymatic Preparation of an R-Amino Acid Intermediate for a γ-Secretase Inhibitor. Org. Process Res. Dev. 2013, 17, 693−700. (f) Sorochinsky, A. E.; Ueki, H.; Aceña, J. L.; Ellis, T. K.; Moriwaki, H.; Sato, T.; Soloshonok, V. A. Chemical deracemization and (S) to (R) interconversion of some fluorine-containing α-amino acids. J. Fluorine Chem. 2013, 152, 114− 118. (g) Vukelić, S.; Ushakov, D. B.; Gilmore, K.; Koksch, B.; Seeberger, P. H. Flow Synthesis of Fluorinated α-Amino Acids. Eur. J. Org. Chem. 2015, 2015, 3036−3039. (h) Kondratov, I. S.; Logvinenko, I. G.; Tolmachova, N. A.; Morev, R. N.; Kliachyna, M. A.; Clausen, F.; Daniliuc, C. G.; Haufe, G. Synthesis and physical chemical properties of 2-amino-4-(trifluoromethoxy)butanoic acid - a CF3O-containing analog of natural lipophilic amino acids. Org. Biomol. Chem. 2017, 15, 672−679. (j) Wang, J.; Lin, D.; Zhou, S.; Soloshonok, V. A.; Liu, H.; et al. Asymmetric Synthesis of Sterically Constrained Linear Trifluoromethyl Containing Amino Acids via Alkylation of Chiral Equivalents of Nucleophilic Glycine and Alanine. J. Org. Chem. 2011, 76, 684−687. (k) Ojima, I.; Hirai, K.; Fujita, M.; Fuchikami, T. New synthetic route to N-acyl α-amino acids via amidocarbonylation by means of homogeneous binary catalyst systems. J. Organomet. Chem. 1985, 279, 203−214. (14) (a) Soloshonok, V. A.; Gerus, I. I.; Yagupolskii, Y. L.; Kukhar, V. P. Fluorine-Containing Amino Acids. III. α-Trifluoromethyl-αAmino Acids. Zh. Org. Khim. 1987, 23, 2308−2313. (b) Soloshonok, V. A.; Ohkura, H.; Yasumoto, M. Operationally Convenient Asymmetric Synthesis of (S)- and (R)-3-Amino-4,4,4-trifluorobutanoic Acid. Part II: Enantioselective Biomimetic Transamination of 4,4,4-Trifluoro-3-oxo-N-[(R)-1-phenylethyl)butanamide. J. Fluorine Chem. 2006, 127, 930−935. (c) Soloshonok, V. A.; Kirilenko, A. G.; Kukhar, V. P.; Resnati, G. Tetrahedron Lett. 1993, 34, 3621−3624. (15) (a) Röschenthaler, G.-V.; Kukhar, V. P.; Kulik, I. B.; Belik, M. Y.; Sorochinsky, A. E.; Rusanov, E. B.; Soloshonok, V. A. Asymmetric
(8) (a) Jäckel, C.; Seufert, W.; Thust, S.; Koksch, B. Evaluation of the molecular interactions of fluorinated amino acids with native polypeptides. ChemBioChem 2004, 5, 717−720. (b) Jäckel, C.; Salwiczek, M.; Koksch, B. Fluorine in a native protein environment how the spatial demand and polarity of fluoroalkyl groups affect protein folding. Angew. Chem., Int. Ed. 2006, 45, 4198−4203. (c) Chiu, H. P.; Suzuki, Y.; Gullickson, D.; Ahmad, R.; Kokona, B.; Fairman, R.; Cheng, R. P. Helix propensity of highly fluorinated amino acids. J. Am. Chem. Soc. 2006, 128, 15556−15557. (d) Chiu, H. P.; Kokona, B.; Fairman, R.; Cheng, R. P. Effect of highly fluorinated amino acids on protein stability at a solvent-exposed position on an internal strand of protein G B1 domain. J. Am. Chem. Soc. 2009, 131, 13192−13193. (e) Salwiczek, M.; Koksch, B. Effects of fluorination on the folding kinetics of a heterodimeric coiled coil. ChemBioChem 2009, 10, 2867−2870. (f) Vagt, T.; Nyakatura, E.; Salwiczek, M.; Jaeckel, C.; Koksch, B. Toward identifying preferred interaction partners of fluorinated amino acids within the hydrophobic environment of a dimeric coiled coil peptide. Org. Biomol. Chem. 2010, 8, 1382−1386. (g) Nyakatura, E. K.; Reimann, O.; Vagt, T.; Salwiczek, M.; Koksch, B. Accommodating fluorinated amino acids in a helical peptide environment. RSC Adv. 2013, 3, 6319−6322. (h) Völler, J. S.; Dulic, M.; Gerling-Driessen, U. I. M.; Biava, H.; Baumann, T.; Budisa, N.; Gruic-Sovulj, I.; Koksch, B. Discovery and investigation of natural editing function against artificial amino acids in protein translation. ACS Cent. Sci. 2017, 3, 73−80. (i) Buer, B. C.; Chugh, J.; Al-Hashimi, H. M.; Marsh, E. N. G. Using fluorine nuclear magnetic resonance to probe the interaction of membrane-active peptides with the lipid bilayer. Biochemistry 2010, 49, 5760−5765. (j) de Kort, D. W.; Rombouts, W. H.; Hoeben, F. J. M.; Janssen, H. M.; Van As, H.; van Duynhoven, J. P. M. Scaling Behavior of Dendritic Nanoparticle Mobility in Semidilute Polymer Solutions. Macromolecules 2015, 48, 7585−7591. (9) Soini, J.; Falschlehner, C.; Liedert, C.; Bernhardt, J.; Vuoristo, J.; Neubauer, P. Norvaline is accumulated after a down-shift of oxygen in Escherichia coli W3110. Microb. Cell Fact. 2008, 7, No. 30. (10) (a) Graham, D. W.; Ashton, W. T.; Barash, L.; Brown, J. E.; Brown, R. D.; Canning, L. F.; Chen, A.; Springer, J. P.; Rogers, E. F. Inhibition of the mammalian β-lactamase renal dipeptidase (dehydropeptidase-I) by Z-2-(acylamino)-3-substituted-propenoic acids. J. Med. Chem. 1987, 30, 1074−90. (b) Tsushima, T.; Kawada, K.; Ishihara, S.; Uchida, N.; Shiratori, O.; Higaki, J.; Hirata, M. Fluorinecontaining amino acids and their derivatives. 7. Synthesis and antitumor activity of α- and γ-substituted methotrexate analogs. Tetrahedron 1988, 44, 5375−5387. (c) Ojima, I.; Jameison, F. A.; Pete, B.; Radunz, H.; Schittenhelm, C.; Lindner, H. J.; Emith, A. E. Design, synthesis and enzyme inhibitory activities of new trifluoromethyl-containing inhibitors for angiotensin converting enzyme. Drug Des. Discovery 1994, 11, 91−113. (d) Hartman, M. C. T.; Josephson, K.; Szostak, J. W. Enzymatic aminoacylation of tRNA with unnatural amino acids. Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 4356− 4361. (e) Shan, W.; Balog, A.; Quesnelle, C.; Gill, P.; Han, W. C.; Norris, D.; Mandal, S.; Thiruvenkadam, R.; Gona, K. B.; Thiyagarajan, K.; Kandula, S.; McGlinchey, K.; Menard, K.; Wen, M. L.; Rose, A.; White, R.; Guarino, V.; Shen, D. R.; Gavai, A. V.; et al. BMS-871: A novel orally active pan-Notch inhibitor as an anticancer agent. Bioorg. Med. Chem. Lett. 2015, 25, 1905−1909. (f) Zhang, Y. K.; Plattner, J. J.; Easom, E. E.; Jacobs, R. T.; Guo, D.; Freund, Y. R.; Berry, P.; Ciaravino, V.; Erve, J. C. L.; Rosenthal, P. J.; et al. Benzoxaborole Antimalarial Agents. Part 5. Lead Optimization of Novel Amide Pyrazinyloxy Benzoxaboroles and Identification of a Preclinical Candidate. J. Med. Chem. 2017, 60, 5889−5908. (g) Oba, T.; Yamamoto, Y.; Nomiyama, S.; Suenaga, H.; Muta, S.; Tashiro, K.; Kuhara, S. Properties of a trifluoroleucine-resistant mutant of Saccharomyces cerevisiae. Biosci., Biotechnol., Biochem. 2006, 70, 1776−1779. (11) (a) Michurin, O. M.; Afonin, S.; Berditsch, M.; Daniliuc, C. G.; Ulrich, A. S.; Komarov, I. V.; Radchenko, D. S. Delivering Structural Information on the Polar Face of Membrane-Active Peptides: 19FNMR Labels with a Cationic Side Chain. Angew. Chem., Int. Ed. 2016, 11850
DOI: 10.1021/acsomega.9b01537 ACS Omega 2019, 4, 11844−11851
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Article
synthesis of phosphonotrifluoroalanine and its derivatives using Ntert-butanesulfinyl imine derived from fluoral. Tetrahedron Lett. 2012, 53, 539−542. (b) Turcheniuk, K. V.; Poliashko, K. O.; Kukhar, V. P.; Rozhenko, A. B.; Soloshonok, V. A.; Sorochinsky, A. E. Efficient asymmetric synthesis of trifluoromethylated β-aminophosphonates and their incorporation into dipeptides. Chem. Commun. 2012, 48, 11519−11521. (16) (a) Soloshonok, V. A.; Tang, X.; Hruby, V. J. Large-Scale Asymmetric Synthesis of Novel Sterically Constrained 2′,6′-Dimethyland α,2′,6′-Trimethyltyrosine and -phenylalanine Derivatives via Alkylation of Chiral Equivalents of Nucleophilic Glycine and Alanine. Tetrahedron 2001, 57, 6375−6382. (b) Soloshonok, V. A.; Tang, X.; Hruby, V. J.; Meervelt, L. V. Asymmetric Synthesis of α,β-Dialkyl-αphenylalanines via Direct Alkylation of a Chiral Alanine Derivative with Racemic α-Alkylbenzyl Bromides. A Case of High Enantiomer Differentiation at Room Temperature. Org. Lett. 2001, 3, 341−343. (c) Qiu, W.; Gu, X.; Soloshonok, V. A.; Carducci, M. D.; Hruby, V. J. Stereoselective synthesis of conformationally constrained reverse turn dipeptide mimetics. Tetrahedron Lett. 2001, 42, 145−148. (17) (a) Han, J.; Nelson, D. J.; Sorochinsky, A. E.; Soloshonok, V. A. Self-Disproportionation of Enantiomers via Sublimation; New and Truly Green Dimension in Optical Purification. Curr. Org. Synth. 2011, 8, 310−317. (b) Ueki, H.; Yasumoto, M.; Soloshonok, V. A. Rational application of self-disproportionation of enantiomers via sublimationa novel methodological dimension for enantiomeric purifications. Tetrahedron: Asymmetry 2010, 21, 1396−1400. (c) Sorochinsky, A. E.; Katagiri, T.; Ono, T.; Wzorek, A.; Aceña, J. L.; Soloshonok, V. A. Optical Purifications via Self-Disproportionation of Enantiomers by Achiral Chromatography: Case Study of a Series of αCF3-containing Secondary Alcohols. Chirality 2013, 25, 365−368. (d) Han, J.; Wzorek, A.; Kwiatkowska, M.; Soloshonok, V. A.; Klika, K. D. The self-disproportionation of enantiomers (SDE) of amino acids and their derivatives. Amino Acids 2019, 51, 865−889. (e) Han, J.; Wzorek, A.; Soloshonok, V. A.; Klika, K. D. The selfdisproportionation of enantiomers (SDE): The effect of scaling down, potential problems versus prospective applications, possible new occurrences, and unrealized opportunities? Electrophoresis 2019, No. 414. (18) (a) Sorochinsky, A. E.; Aceña, J. L.; Moriwaki, H.; Sato, T.; Soloshonok, V. A. 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, 1017−1033. (b) Aceña, J. L.; Sorochinsky, A. E.; Soloshonok, V. A. 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, 2047−2073. (c) Wang, Y.; Song, X.; Wang, J.; Moriwaki, H.; Soloshonok, V. A.; Liu, H. Recent approaches for asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes. Amino Acids 2017, 49, 1487− 1520. (19) (a) Ellis, T. K.; Ueki, H.; Yamada, T.; Ohfune, Y.; Soloshonok, V. A. The Design, Synthesis and Evaluation of a New Generation of Modular Nucleophilic Glycine Equivalents for the Efficient Synthesis of Sterically Constrained α-Amino Acids. J. Org. Chem. 2006, 71, 8572−8578. (b) Soloshonok, V. A.; Ueki, H.; Ellis, T. K.; Yamada, T.; Ohfune, Y. Application of Modular Nucleophilic Glycine Equivalents for Truly Practical Asymmetric Synthesis of β-Substituted Pyroglutamic Acids. Tetrahedron Lett. 2005, 46, 1107−1110. (20) Romoff, T. T.; Palmer, A. B.; Mansour, N.; Creighton, C. J.; Miwa, T.; Ejima, Y.; Moriwaki, H.; Soloshonok, V. A. Scale-up Synthesis of (R)- and (S)-N-(2-benzoyl-4-chlorophenyl)-1-(3,4dichlorobenzyl)pyrrolidine-2-carboxamide hydrochloride, a Versatile Reagent for Preparation of Tailor-made α- and β-Amino Acids in Enantiomerically Pure Form. Org. Process Res. Dev. 2017, 21, 732− 739. (21) Nian, Y.; Wang, J.; Moriwaki, H.; Soloshonok, V. A.; Liu, H. Analysis of crystallographic structures of Ni(II) complexes of α-amino
acid Schiff bases; Elucidation of the substituents effect on stereochemical preferences. Dalton Trans. 2017, 46, 4191−4198. (22) (a) Soloshonok, V. A.; Sorochinsky, A. E. Practical Methods for the Synthesis of Symmetrically α,α-Disubstituted-α-Amino Acids. Synthesis 2010, 2319−2344. (b) Tang, X.; Soloshonok, V. A.; Hruby, V. J. Convenient Asymmetric Synthesis of Enantiomerically Pure 2′,6′-Dimethyltyrosine (DMT) via Alkylation of Chiral Nucleophilic Glycine Equivalent. Tetrahedron: Asymmetry 2000, 11, 2917−2925. (23) (a) Takeda, R.; Kawamura, A.; Kawashima, A.; Sato, T.; Moriwaki, H.; Izawa, K.; Akaji, K.; Wang, S.; Liu, H.; Aceña, J. L.; Soloshonok, V. A. Chemical Dynamic Kinetic Resolution and (S)/ (R)-Interconversion of Unprotected α-Amino Acids. Angew. Chem., Int. Ed. 2014, 53, 12214−12217. (b) Sorochinsky, A. E.; Ueki, H.; Aceña, J. L.; Ellis, T. K.; Moriwaki, H.; Soloshonok, V. A.; et al. Chemical approach for interconversion of (S)- and (R)-α-amino acids. Org. Biomol. Chem. 2013, 11, 4503−4507. (24) (a) Soloshonok, V. A.; Ellis, T. K.; Ueki, H.; Ono, T. Resolution/Deracemization of Chiral α-Amino Acids Using Resolving Reagents with Flexible Stereogenic Centers. J. Am. Chem. Soc. 2009, 131, 7208−7209. (25) Zhou, S.; Wang, J.; Chen, X.; Aceña, J. L.; Soloshonok, V. A.; Liu, H. Chemical Kinetic Resolution of Unprotected β-Substituted-βAmino Acids Using Recyclable Chiral Ligands. Angew. Chem., Int. Ed. 2014, 53, 7883−7886. (26) (a) Soloshonok, V. A.; Ueki, H. Design, Synthesis and Characterization of Binuclear Ni(II) Complexes with Inherent Helical Chirality. J. Am. Chem. Soc. 2007, 129, 2426−2427. (b) Soloshonok, V. A.; Ono, T.; Ueki, H.; Vanthuyne, N.; Balaban, T. S.; Bürck, J.; Fliegl, H.; Klopper, W.; Naubron, J. V.; Tam, T. T.; Drake, A. F.; Roussel, C. Ridge-tile-like chiral topology: Synthesis, resolution and complete chiroptical characterization of enantiomers of edge-sharing binuclear square planar complexes of Ni(II) bearing achiral ligands. J. Am. Chem. Soc. 2010, 132, 10477−10483.
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DOI: 10.1021/acsomega.9b01537 ACS Omega 2019, 4, 11844−11851
