137.54, 131.25, 128.97,J Org Chem. Author manuscript; available in PMC 2014 November 01.Walia et al.Page127.72, 127.13, 125.09, 120.14, 118.57, 66.28, 46.54, 32.19, 21.03; LRMS (ESI): m/z = 359.17 [M + H]+. The information had been in accordance with those previously reported.NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author Manuscript2-(4-(two,5-Dimethyl-1H-pyrrol-1-yl)phenyl)ethanamine HCl (16)–Using system B, starting material 15 was converted towards the intermediate 2-(4-(2,5-dimethyl-1H-pyrrol-1yl)phenyl)acetonitrile. The information have been in accordance with those previously reported.27 Yield: 862 mg (86 ); white crystal, mp: 102 – 104 ; Rf = 0.six (EtOAc/hexanes, 1:eight); 1H NMR (500 MHz, CDCl3) 7.48 (d, J = eight.three Hz, 2H), 7.28 (d, J = 8.3 Hz, 2H), 5.95 (s, 2H), three.87 (s, 2H), 2.06 (s, 6H); 13C NMR (126 MHz, CDCl3) 138.91, 129.42, 128.95, 128.80, 128.75, 117.64, 106.06, 23.38, 13.07. Right after mixing this intermediate (0.210 g, 1 mmol) with Raney Nickel (0.1 mL, 50 in water) in ethanol (30 ml), the mixture was stirred below hydrogen balloon at area temperature for 2 h. The reaction mixture was filtered by using membrane filter (25 mm, 0.22 PVDF), and also the filtrate was concentrated in vacuum to offer colorless oil. This oil was dissolved in hydrochloric acid in methanol and re-concentrated in vacuum to offer 16 as pale yellow HCl salt. (93 ). This amine HCl salt was utilized directly inside the next step without the need of further purification. 1H NMR (500 MHz, CDCl3) eight.54 (bs, 3H), 7.36 (d, J = 7.9 Hz, 2H), 7.19 (d, J = 7.9 Hz, 2H), 5.91 (s, 2H), 3.45 – 3.29 (m, 2H), 3.27 – 3.15 (m, 2H), two.05 (s, 6H); 13C NMR (126 MHz, CDCl3) 138.two, 135.4, 129.five, 128.8, 105.9, 41.1, 33.four, 13.1; HRMS (ESI-TOF) m/z: [M + H ]+ Calcd for C14H19N2 215.1548, Identified 215.1540. Compounds 17a-c have been synthesized using following approach from compound 16: To a dry 25 mL round bottom flask equipped using a magnetic stir bar was added Compound 16 (0.1-Phenylbuta-2,3-dien-1-one web 200 g, 1 mmol) dissolved in dichloromethane (15 mL). Boc2O (0.23 mL, 1.two mmol), CbzCl (0.143 mL, 1.two mmol), or Fmoc-OSu (0.337 g, 1.2 mmol) had been added to the mixture depending on if 17a, 17b, or 17c was preferred, respectively. Triethylamine (0.028 mL, 1.two mmol) was also added dropwise towards the reaction mixture to deprotonate the HCl salt. The reaction mixture was stirred at space temperature for four h after which concentrated by rotary evaporation. The resulting yellow oil was purified by flash column chromatography employing a 25 g silica gel cartridge to offer the protected amine. tert-Butyl 4-(two,5-dimethyl-1H-pyrrol-1-yl)phenethylcarbamate (17a)–Yield 249 mg (79 ); white crystals; mp = 170-172 ; Rf = 0.3-Fluoro-L-tyrosine In stock 3 (EtOAc/hexanes, 1:15-1:6); 1H NMR (500 MHz, CDCl3) 7.PMID:25016614 29 (d, J = eight.0 Hz, 2H), 7.15 (d, J = 8.1 Hz, 2H), five.90 (s, 2H), four.71 (m, 1H), three.49 – 3.35 (m, 2H), two.92 – 2.80 (m, 2H), 2.04 (s, 6H), 1.52 – 1.42 (s, 9H); 13C NMR (126 MHz, CDCl3) 155.9, 138.six, 137.2, 129.four, 128.8, 128.three, 105.6, 79.3, 41.7, 36.0, 28.five, 13.1; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C19H26N2NaO2 337.1886, Identified 337.1893. Benzyl 4-(two,5-dimethyl-1H-pyrrol-1-yl)phenethylcarbamate (17b)–Yield 280 mg (86 ); clear oil; Rf = 0.three (EtOAc/hexanes, 1:15-1:six); 1H NMR (500 MHz, CDCl3) 7.47 7.35 (m, 5H), 7.32 – 7.25 (m, 2H), 7.21 – 7.14 (m, 2H), five.94 (s, 2H), five.15 (s, 2H), four.90 (m, 1H), three.58 – 3.49 (q, J = six.eight Hz, 2H), 2.96 – two.87 (t, J = 7.0 Hz, 2H), two.06 (s, 6H); 13C NMR (126 MHz, CDCl3) 156.three, 138.two, 137.four, 136.five, 129.4, 128.9, 128.6, 128.four, 128.3, 128.two, 105.six, 66.eight, 42.1, 35.eight, 13.1; HRMS (ESI-TOF).