Synlett 2012; 23(12): 1759-1764
DOI: 10.1055/s-0031-1290381
letter
© Georg Thieme Verlag Stuttgart · New York

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
Further Information

Publication History

Received: 16 April 2012

Accepted after revision: 26 April 2012

Publication Date:
21 June 2012 (online)


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.

Supporting Information

 
  • References and Notes

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  • 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 3aq
  • 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