## 3 Materials and Methods
### Analytics of the Synthesized Compounds
2-chloro-4-(3-nitrophenyl)pyrimidine (30): Yield: 79%; yellow solid; Mp 123-125 \({}^{\circ}\)C; NMR (400 MHz, CDCl\({}_{3}\)): \(\delta\) (ppm) = 7.74 (t, \(J\) = 8.0 Hz, 1H), 7.76 (d, \(J\) = 5.2 Hz, 1H), 8.41 (ddd, \(J_{1}\) = 1.1 Hz, \(J_{2}\) = 2.2 Hz, \(J_{3}\) = 8.2 Hz, 1H), 8.48 (ddd, \(J_{1}\) = 1.1 Hz, \(J_{2}\) = 1.8 Hz, \(J_{3}\) = 7.8 Hz, 1H), 8.76 (d, \(J\) = 5.2 Hz, 1H), 8.93 (t, \(J\) = 1.9 Hz, 2H) as reported [45]; \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)): \(\delta\) (ppm) = 11546, 122.46, 126.40, 130.48, 133.26, 136.96, 149.01, 160.77, 162.37, 164.64; HRMS (ESI+) \(m/z\) calc. for C\({}_{10}\)H\({}_{7}\)O\({}_{3}\)N\({}_{2}\)Cl [M + H]\({}^{+}\) 236.0221, found 236.0221; HPLC \(t_{R}\) = 6.33 min; Rf = 0.17 (EtOAc/n-Hex, 1:2, _v/v_). 3-(2-chlorophenyl)pyrimidine-4-yl)benzizdite (32): Yield: 83%; pale pink solid; Mp 180-182 \({}^{\circ}\)C; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)): \(\delta\) (ppm) = 7.64-7.68 (m, 1H), 7.68 (d, \(J\) = 5.2 Hz, 1H), 7.83 (dtd, \(J_{1}\) = 1.4 Hz, \(J_{2}\) = 7.7 Hz, 1H), 8.83 (ddd, \(J_{1}\) = 1.2 Hz, \(J_{2}\) = 1.91H), 8.20 (dt, \(J_{1}\) = 1.4 Hz, \(J_{2}\) = 7.8 Hz, 1H), 8.34 (ddd, \(J_{1}\) = 1.2 Hz, \(J_{2}\) = 1.9 Hz, \(J_{3}\) = 7.9 Hz, 1H), 8.68 (d, \(J\) = 5.3 Hz, 1H), 8.69-8.70 (m, 1H) as reported [48]; \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)): 8 (ppm) = 52.58, 115.42, 128.57, 129.52, 131.30, 131.88, 132.86, 135.61, 160.28, 162.13, 166.24, 166.43; HRMS (ESI+) \(m\)/\(\varepsilon\) calc. for C\({}_{12}\)H\({}_{10}\)O\({}_{2}\)N\({}_{2}\)Cl [M + H]\({}^{+}\) 249.0425, found 249.0424; HPLC \(t_{R}\) = 6.29 min; Rf = 0.25 (EtOAc/n-Hex, 12, \(v\)/\(v\)). _3-(2-chlorophenyloryprimidin-4-yl)benzoic acid (34)_: Yield: 55%; white solid; Mp 196-198 \({}^{\circ}\)C; \({}^{1}\)H NMR (400 MHz, DMSO\({}_{d}\)): 8 (ppm) = 7.49 (t, \(J\) = 7.7 Hz, 1H), 8.12-8.16 (m, 3H), 8.72-8.74 (m, 1H), 8.76 (d, \(J\) = 5.3 Hz, 1H), 1H from COOH is exchanged as reported [47]; \({}^{13}\)C NMR (100 MHz, DMSO-\(d_{d}\)): 8 (ppm) = 116.07, 128.19, 128.28, 132.80, 133.70, 140.01, 160.51, 161.08, 166.51, 169.84; HRMS (ESI-) \(m\)/\(\varepsilon\) calc. for C\({}_{11}\)H\({}_{\rm o}\)O\({}_{2}\)N\({}_{2}\)Cl [M \(-\) H]\({}^{-}\) 233.0123, found 233.0122; HPLC \(t_{R}\) = 4.96 min; Rf = 0.14 (DCM/MeOH, 9:1, \(v\)/\(v\)). _3-(2-chlorophenyloryprimidin-4-yl)aniline (35)_: Yield: 55%; yellow solid; Mp 120-122 \({}^{\circ}\)C (lit. 137-138 \({}^{\circ}\)C [49]); \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)): 8 (ppm) = 3.86 (s, 2H), 6.85 (ddd, \(J_{1}\) = 1.0 Hz, \(J_{2}\) = 2.4 Hz, \(J_{3}\) = 7.9 Hz, 1H), 7.28 (t, \(J\) = 7.9 Hz, 1H), 7.38 (ddd, \(J_{1}\) = 1.0 Hz, \(J_{2}\) = 1.8 Hz, \(J_{3}\) = 7.9 Hz, 1H), 7.48 (t, \(J\) = 2.0 Hz, 1H), 7.60 (d, \(J\) = 5.3 Hz, 1H), 8.61 (d, \(J\) = 5.3 Hz, 1H); \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)): 8 (ppm) = 113.67, 115.41, 117.61, 118.60, 130.15, 136.21, 147.37, 159.83, 161.86, 167.51; HRMS (ESI+) \(m\)/\(\varepsilon\) calc. for C\({}_{10}\)H\({}_{9}\)N\({}_{3}\)Cl [M + H]\({}^{+}\) 206.0480, found 206.0478; HPLC \(t_{R}\) = 3.35 min; Rf = 0.23 (EtOAc/n-Hex, 1:1, \(v\)/\(v\)). _2-chloro-4-(4-fluorophenyl)pyrimidine (36)_: Yield: 62%; white solid; Mp 101-103 \({}^{\circ}\)C; \({}^{1}\)H NMR (400 MHz, CDCl\({}_{3}\)): 8 (ppm) = 7.18-7.24 (m, 2H), 7.61 (d, \(J\) = 5.3 Hz, 1H), 8.10-8.15 (m, 2H), 8.64 (d, \(J\) = 5.3 Hz, 1H); \({}^{13}\)C NMR (100 MHz, CDCl\({}_{3}\)): 8 (ppm) = 114.91, 116.47 (d, \(J\)\({}_{C-F}\) = 22.0 Hz), 129.82 (d, \(J_{C-F}\) = 8.9 Hz), 131.37, 160.06, 162.07, 162.25 (d, \(J_{C-F}\) = 253.3 Hz), 166.62; HRMS (ESI+) \(m\)/\(\varepsilon\) calc. for C\({}_{10}\)H\({}_{7}\)N\({}_{2}\)ClF [M + H]\({}^{+}\) 209.0276, found 209.0278; HPLC \(t_{R}\) = 6.44 min; Rf = 0.31 (EtOAc/n-Hex, 1:3, \(v\)/\(v\)).