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

Ciputra Tejo; Hui Quan Yeo; Philip Wai Hong Chan

doi:10.1055/s-0033-1340108

Synlett, Inhaltsverzeichnis

Synlett 2014; 25(2): 201-204
DOI: 10.1055/s-0033-1340108

letter

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

Authors

Ciputra Tejo

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore Fax: +6567911961 eMail: waihong@ntu.edu.sg
Hui Quan Yeo

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore Fax: +6567911961 eMail: waihong@ntu.edu.sg
Philip Wai Hong Chan*

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore Fax: +6567911961 eMail: waihong@ntu.edu.sg

Abstract

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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

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Referenzen

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

Zusatzmaterial

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