Brønsted Acid Catalyzed Amination of 1,3-Dicarbonyl Compounds by Iminoiodanes

Abstract

A synthetic method to aminate 1,3-dicarbonyl compounds with PhI=NTs using Brønsted acid catalysis is described herein. The method was shown to be applicable to β-keto esters and phosphonates as well as 1,3-diones, providing the corresponding α,α-acyl amino acid derivatives in moderate to excellent yields.

Key words

α,α-acyl amino acid derivatives - iminoiodanes - amination - Brønsted acid catalysis - 1,3-dicarbonyl compounds

• References and Notes


Selected recent reviews:
• 1a So SM, Kim H, Mui L, Chin J. Eur. J. Org. Chem. 2012; 229
• 1b Perdih A, Sollner Dolenc M. Curr. Org. Chem. 2011; 15: 3750
• 1c Kudzin ZH, Kudzin MH, Drabowicz J, Stevens CV. Curr. Org. Chem. 2011; 15: 2015
• 1d Naydenova E, Todorov P, Troev K. Amino Acids 2010; 38: 23

Selected recent examples:
• 2a Pandey AK, Naduthambi D, Thomas KM, Zondlo NJ. J. Am. Chem. Soc. 2013; 135: 4333
• 2b Brasile G, Mauri L, Sonnino S, Compostella F, Ronchetti F. Amino Acids 2013; 44: 435
• 2c Ton TM. U, Himawan F, Chang JW. W, Chan PW. H. Chem. Eur. J. 2012; 18: 12020
• 2d Weber M, Frey W, Peters R. Adv. Synth. Catal. 2012; 354: 1443
• 2e Jiang C, Covell DJ, Stepan AF, Plummer MS, White MC. Org. Lett. 2012; 14: 1386
• 2f Yu L, Liu S.-S, Cui J, Hou X.-S, Zhang C. Org. Lett. 2012; 14: 832
• 2g Tosatti P, Campbell AJ, House D, Nelson A, Marsden SP. J. Org. Chem. 2011; 76: 5495
• 2h Tsubogo T, Kano Y, Ikemoto K, Yamashita Y, Kobayashi S. Tetrahedron: Asymmetry 2010; 21: 1221
• 2i Hartmann CE, Baumann T, Bächle M, Bräse S. Tetrahedron: Asymmetry 2010; 21: 1341
• 2j Scott WL, Zhou Z, Zajdel P, Pawłowski M, O’Donnell MJ. Molecules 2010; 15: 4961
• 2k Baumann T, Bächle M, Bräse S. Org. Lett. 2006; 8: 3797

Selected general reviews on transition-metal-mediated imido/nitrene reactions:
• 3a Dequirez G, Pons V, Dauban P. Angew. Chem. Int. Ed. 2012; 51: 7384
• 3b Roizen JL, Harvey ME, Du Bois J. Acc. Chem. Res. 2012; 45: 911
• 3c Collet F, Lescot C, Dauban P. Chem. Soc. Rev. 2011; 40: 1926
• 3d Chang JW. W, Ton TM. U, Chan PW. H. Chem. Rec. 2011; 11: 331
• 3e Collet F, Dodd RH, Dauban P. Chem. Commun. 2009; 5061
• 3f Díaz-Requejo MM, Pérez PJ. Chem. Rev. 2008; 108: 3379
• 3g Davies HM. L, Manning JR. Nature (London) 2008; 451: 417
• 3h Davies HM. L. Angew. Chem. Int. Ed. 2006; 45: 6422
• 3i Müller P, Fruit C. Chem. Rev. 2003; 103: 2905

Selected recent examples on transition-metal-mediated imido/nitrene reactions:
• 4a Wang J, Frings M, Bolm C. Angew. Chem. Int. Ed. 2013; 52: 8661
• 4b Gava R, Biffis A, Tubaro C, Zaccheria F, Ravasio N. Catal. Commun. 2013; 40: 63
• 4c Jin L.-M, Xu X, Lu H, Cui X, Wojtas L, Zhang XP. Angew. Chem. Int. Ed. 2013; 52: 5309
• 4d Beltrán Á, Lescot C, Díaz-Requejo MM, Pérez PJ, Dauban P. Tetrahedron 2013; 69: 4488
• 4e Maestre L, Sameera WM. C, Díaz-Requejo MM, Maseras F, Pérez PJ. J. Am. Chem. Soc. 2012; 135: 1338
• 4f Yoshimura A, Nemykin VN, Zhdankin VV. Chem. Eur. J. 2011; 17: 10538
• 4g Liu Y, Che C.-M. Chem. Eur. J. 2010; 16: 10494
• 4h Nakanishi M, Salit A.-F, Bolm C. Adv. Synth. Catal. 2008; 350: 1835
• 4i Anada M, Tanaka M, Washio T, Yamawaki M, Abe T, Hashimoto S. Org. Lett. 2007; 9: 4559
• 4j Fructos MR, Trofimenko S, Díaz-Requejo MM, Pérez PJ. J. Am. Chem. Soc. 2006; 128: 11784

For selected recent examples from our group, see ref. 2c and:
• 5a Ton TM. U, Tejo C, Tiong DL. Y, Chan PW. H. J. Am. Chem. Soc. 2012; 134: 7344
• 5b Ton TM. U, Tejo C, Chang JW. W, Chan PW. H. J. Org. Chem. 2011; 76: 4894
• 5c Chang JW. W, Ton TM. U, Tania S, Taylor PC, Chan PW. H. Chem. Commun. 2010; 46: 922
• 5d Chang JW. W, Ton TM. U, Zhang Z, Xu Y, Chan PW. H. Tetrahedron Lett. 2009; 50: 161
• 5e Chang JW. W, Chan PW. H. Angew. Chem. Int. Ed. 2008; 47: 1138

For selected recent examples on transition-metal-free reactions with nitrenoid precursors, see:
• 6a Kiyokawa K, Kosaka T, Minakata S. Org. Lett. 2013; 15: 4858
• 6b Souto JA, Martínez C, Velilla I, Muñiz K. Angew. Chem. Int. Ed. 2013; 52: 1324
• 6c Ochiai M, Yamane S, Hoque MM, Saito M, Miyamoto K. Chem. Commun. 2012; 48: 5280
• 6d Takeda Y, Hayakawa J, Yano K, Minakata S. Chem. Lett. 2012; 41: 1672
• 6e Ochiai M, Miyamoto T, Kaneaki K, Hayashi S, Nakanishi W. Science 2011; 332: 448
• 6f Kowalczyk R, Edmunds AJ. F, Hall RG, Bolm C. Org. Lett. 2011; 13: 768
• 6g Zhang D.-H, Wei Y, Shi M. Eur. J. Org. Chem. 2011; 4940
• 6h Karabal PU, Chouthaiwale PV, Shaikh TM, Suryavanshi G, Sudalai A. Tetrahedron Lett. 2010; 51: 6460
• 6i Fang C, Qian W, Bao W. Synlett 2008; 2529
• 6j Li J, Chan PW. H, Che C.-M. Org. Lett. 2005; 7: 5801
• 6k Lim B.-W, Ahn K.-H. Synth. Commun. 1996; 26: 3407
• 7 General Procedure To a degassed mixture of PhI=NTs (0.6 mmol, 224 mg) and powdered 4 Å MS (240 mg) was added CH₂Cl₂ (1 mL). The reaction was cooled to 0 °C, and a solution of TFA (0.05 mmol, 3.83 μL) in CH₂Cl₂ (1 mL) was added. The 1,3-dicarbonyl compound was added, and the reaction was monitored by TLC analysis. Upon completion, the reaction mixture was filtered, washed with EtOAc (40 mL), concentrated under reduced pressure, and purified by flash chromatography [n-hexane–EtOAc (4:1) as eluent] to furnish the title compound.
• 8 Representative Experimental Data Ethyl 2-(4-Methylphenylsulfonamido)-3-oxo-3-phenylpropanoate (2a) Reaction time = 1.5 h; yield 86%; 0.162 g; white solid. ¹H NMR (400 MHz, CDCl₃): δ = 7.98 (d, J = 7.4 Hz, 2 H), 7.73 (d, J = 8.3 Hz, 2 H), 7.62 (t, J = 7.4 Hz, 1 H), 7.47 (t, J = 7.7 Hz, 2 H), 7.24 (d, J = 8.1 Hz, 2 H), 6.00 (d, J = 8.9 Hz, 1 H), 5.58 (d, J = 8.9 Hz, 1 H), 3.97 (q, J = 7.1 Hz, 2 H), 2.38 (s, 3 H), 1.04 (t, J = 7.1 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 190.2, 165.9, 144.1, 144.0, 136.6, 134.7, 129.8, 129.5, 128.9, 127.4, 62.6, 60.9, 21.6, 13.8. Ethyl 3-(4-Bromophenyl)-2-(4-methylphenyl-sulfonamido)-3-oxopropanoate (2h) Reaction time = 1.5 h; yield 60%; 0.114 g; white solid. ¹H NMR (400 MHz, CDCl₃): δ = 7.86 (d, J = 7.2 Hz, 2 H), 7.72 (d, J = 8.3 Hz, 2 H), 7.62 (d, J = 8.7 Hz, 2 H), 7.25 (d, J = 8.2 Hz, 2 H), 5.96 (d, J = 8.7 Hz, 1 H), 5.52 (d, J = 8.7 Hz, 1 H), 4.02–3.93 (m, 2 H), 2.39 (s, 3 H), 1.05 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 189.6, 165.9, 144.2, 136.5, 132.3, 130.9, 130.2, 129.8, 127.4, 62.9, 60.9, 21.6, 13.8. N-(2,4-Dioxopentan-3-yl)-4-methylbenzenesulfonamide (2s) Reaction time = 2 h; yield 62%; 0.0840 g; yellow solid. ¹H NMR (300 MHz, CDCl₃): δ = 16.3 (s, 1 H), 7.84 (s, 1 H), 7.71 (d, J = 8.1 Hz, 2 H), 7.32 (d, J = 8.1 Hz, 2 H), 6.16 (s, 1 H), 5.16 (s, 1 H), 2.44 (s, 3 H), 1.87 (s, 6 H). ¹³C NMR (75 MHz, CDCl₃): δ = 194.1, 144.3, 136.6, 130.1, 127.4, 110.1, 22.1, 21.6.
• 9a Arnett EM, Maroldo SG, Schilling SL, Harrelson JA. J. Am. Chem. Soc. 1984; 106: 6759
• 9b Olmstead WN, Bordwell FG. J. Org. Chem. 1980; 45: 3299

Refer to ref. 2f and:
• 10a Moriarty RM. J. Org. Chem. 2005; 70: 2893
• 10b Ochiai M, Suefuji T, Miyamoto K, Shiro M. Org. Lett. 2005; 7: 2893
• 11a Hansch C, Leo A, Taft RW. Chem. Rev. 1991; 91: 165
• 11b Hammett LP. J. Am. Chem. Soc. 1937; 59: 96
• 12 Kwong H.-L, Lee W.-S. Tetrahedron: Asymmetry 2000; 11: 2299