Regiospecific Direct C–H Arylation at the 2-Position of l-Histidine Using Arylboronic Acids

Amit Mahindra; Rahul Jain

doi:10.1055/s-0031-1290381

Synlett, Table of Contents

Synlett 2012; 23(12): 1759-1764
DOI: 10.1055/s-0031-1290381

letter

Regiospecific Direct C–H Arylation at the 2-Position of l-Histidine Using Arylboronic Acids

Amit Mahindra

Department of Medicinal Chemistry, National Institute of Pharmaceutical Education and Research, Sector 67, S.A.S. Nagar, Punjab 160 062, India, Fax: +91(172)2214692 Email: rahuljain@niper.ac.in

,

Rahul Jain*

Department of Medicinal Chemistry, National Institute of Pharmaceutical Education and Research, Sector 67, S.A.S. Nagar, Punjab 160 062, India, Fax: +91(172)2214692 Email: rahuljain@niper.ac.in

› Author Affiliations

Abstract

All articles of this category

Abstract

The first regiospecific direct C-2 arylation procedure for histidine using arylboronic acids has been developed. The reaction allows a one-step synthesis of a large variety of 2-aryl-l-histidines using ammonium persulfate and catalytic silver nitrate in TFA and CH₂Cl₂/H₂O (1:1) at ambient temperature.

Key words

regiospecific - arylation - histidine - arylboronic acids - C–H activation

Full Text

References

References and Notes

1a Rivier J, Vale W, Monahan M, Ling N, Burgus R. J. Med. Chem. 1972; 15: 479
1b Jain R, Cohen LA, El Kadi NA, King MM. Tetrahedron 1997; 53: 2365
1c Haug BE, Stenson W, Stiberg T, Svendsen JS. J. Med. Chem. 2004; 47: 4159
1d Monga V, Meena CL, Rajput S, Pawar S, Sharma SS, Lu X, Gershengorn MC, Jain R. ChemMedChem 2011; 6: 531

2a Kaur N, Lu X, Gershengorn MC, Jain R. J. Med. Chem. 2005; 48: 6162
2b van Kan EJ. M, van der Bent A, Demel RA, de Kruijff B. Biochemistry 2001; 40: 6398
2c Delort E, Nguyen-Trung NQ, Darbre T, Reymond JL. J. Org. Chem. 2006; 71: 4468
2d Sharma RK, Reddy RP, Tegge W, Jain R. J. Med. Chem. 2009; 52: 7421

3a Maibaum J, Rich DH. J. Med. Chem. 1988; 31: 625
3b Samanen J, Brandeis E, Narindray D, Adams W, Cash T, Yellin T, Regoli D. J. Med. Chem. 1988; 31: 737
3c Raddatz P, Jonczyk A, Minck KO, Schmitges CJ, Sombroek J. J. Med. Chem. 1991; 34: 3267
3d Mao Z, Pan J, Kalman TI. J. Med. Chem. 1996; 39: 4340

4a Jones JH, Rathbone DL, Wyatt PB. Synthesis 1987; 1110
4b Yue W, Lewis SI, Koen YM, Hanzlik RP. Bioorg. Med. Chem. Lett. 2004; 14: 1637
4c DalZotto C, Michaux J, Martinand-Lurin E, Campagne JM. Eur. J. Org. Chem. 2010; 3811
4d Qian W, Liu F, Burke TR. Jr. J. Org. Chem. 2011; 76: 8885

5a Bellina F, Cauteruccio S, Mannina L, Rossi R, Viel S. J. Org. Chem. 2005; 70: 3997
5b Bellina F, Cauteruccio S, Mannina Bellina F, Cauteruccio S, Rossi R. Tetrahedron 2007; 63: 4571
5c Shibahara F, Yamaguchi E, Murai T. J. Org. Chem. 2011; 76: 2680

6a Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
6b Cerezo V, Afonso A, Planas M, Feliu L. Tetrahedron 2007; 63: 10445

7a Godula K, Sames D. Science 2006; 312: 67
7b Bellina F, Cauteruccio S, Mannina L, Rossi R, Viel S. Eur. J. Org. Chem. 2006; 693
7c Ackermann L, Vicente R, Kapdi AR. Angew. Chem. Int. Ed. 2009; 48: 9792
7d Joo JM, Toure BB, Sames D. J. Org. Chem. 2010; 75: 4911
7e Kwak J, Kim M, Chang S. J. Am. Chem. Soc. 2011; 133: 3780

8 Skoumbourdis AP, Moore S, Landsman M, Thomas CJ. Tetrahedron Lett. 2007; 48: 9140

9a Seiple IB, Su S, Rodriguez RA, Gianatassio R, Fujiwara Y, Sobel AL, Baran PS. J. Am. Chem. Soc. 2010; 132: 13194
9b Fujiwara Y, Domingo V, Seiple IB, Gianatassio R, Del Bel M, Baran PS. J. Am. Chem. Soc. 2011; 133: 3295
9c Ji Y, Brueckl T, Baxter RD, Fujiwara Y, Seiple IB, Su S, Blackmond DG, Baran PS. Proc. Natl. Acad. Sci. U.S.A. 2011; 108: 14411

10a Minisci F. Synthesis 1973; 1
10b Minisci F, Vismara E, Fontana F. Heterocycles 1989; 28: 489
10c Duncton MA. J. Med. Chem. Commun. 2011; 2: 1135

11 Heinisch G, Lotsch G. Angew. Chem., Int. Ed. Engl. 1985; 24: 692
12 General Experimental Procedure To a solution of 1a (1.89 mmol, 1.0 equiv) in CH₂Cl₂ (5 mL), TFA (2.83 mmol, 1.5 equiv) was added. After 5 min a solution of AgNO₃ (0.37 mmol, 0.2 equiv) in H₂O (5 mL) was added, followed by arylboronic acid (3.77 mmol, 2 equiv). Ammonium persulfate (3.77 mmol, 2.0 equiv) was then added in one portion, and the solution was stirred vigorously at r.t. for 10–18 h and monitored by TLC analysis of the organic layer. Upon the completion of reaction, the reaction pH was adjusted around 11–12 by the addition of NH₃ solution. The residual CH₂Cl₂ was evaporated, followed by dilution with H₂O, and extracted with EtOAc. The layers were separated, and the organic layer was washed with a mixture of H₂O and brine. The resulting organic solution was dried over Na₂SO₄ and filtered. The filtrate was concentrated, and the residue was purified by flash column chromatography to provide 3a–q
13 Analytical Data of N-α-Trifluoroacetyl-2-phenyl-l-histidine Methyl Ester (3a) Yield 45%; yellow semisolid. ¹H NMR (400 MHz, CDCl₃): δ = 9.87 (br s, 1 H), 7.72 (dd, J = 1.5, 8.0 Hz, 2 H), 7.34–7.26 (m, 3 H), 6.75 (s, 1 H), 4.78 (t, J = 4.5 Hz, 1 H), 3.61 (s, 3 H), 3.16 (dd, J = 4.8, 15.1 Hz, 1 H), 3.06 (dd, J = 4.6, 14.9 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 170.4, 158.1, 146.7, 141.4, 135.7, 129.4, 127.6, 125.2, 120.2, 117.3, 115.4, 111.6, 52.9, 29.6, 27.9. IR (neat): ν = 3289, 1949, 1715, 1557, 1464, 1411, 1214, 967, 773, 698 cm^–1. HRMS (ESI-TOF): m/z calcd for [M + H⁺]: 342.1065; found: 342.1078
14 Analytical Data of N-α-Trifluoroacetyl-2-(4-methylphenyl)-l-histidine Methyl Ester (3d) Yield 52%; yellow semisolid. ¹H NMR (400 MHz, CDCl₃): δ = 9.79 (br s, 1 H), 7.62–7.61 (m, 2 H), 7.26–7.18 (m, 2 H), 6.76 (s, 1 H), 4.81 (s, 1 H), 3.66 (s, 3 H), 3.21 (dd, J = 4.4, 14.9 Hz, 1 H), 3.09 (dd, J = 0.8, 4.8, 15.0 Hz, 1 H), 2.35 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 170.4, 158.0, 156.9, 146.9, 139.0, 136.0, 129.5, 126.6, 124.8, 117.4, 114.7, 111.7, 52.8, 52.7, 28.0, 21.2. IR (neat): ν = 3302, 2926, 1749, 1559, 1439, 1181, 821, 729 cm^–1. HRMS (ESI-TOF): m/z calcd for [M + H⁺]: 356.1222; found: 356.1220

Supplementary Material

Supporting Information