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

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

• 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 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