C(N)C1C=CC=CC=1.C(=O)(O[CH2:13][CH:14]=[CH:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)OC.[NH2:23][C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1>CC1(C)C(C=CC2CCC/C(=C/C=C3/C(C)(C)C4C(N/3CCCCS(O)(=O)=O)=CC=CC=4)/C=2OC2C=CC(OCCCCNCC3OC(O)C(N)C(O)C3O)=CC=2)=[N+](CCCCS([O-])(=O)=O)C2C1=CC=CC=2.C(Cl)(Cl)Cl>[C:16]1([CH:15]([C:24]2([NH2:23])[CH:29]=[CH:28][CH:27]=[CH:26][CH2:25]2)[CH:14]=[CH2:13])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1By the procedure for reaction of benzylamine with methyl cinnamyl carbonate, the reaction of aniline (130 mg, 1.40 mmol) and methyl cinnamyl carbonate (188 mg, 0.980 mmol) with [(COD)Ir(κ2-L1)L1] (Ir-2) (13.8 mg, 0.0100 mmol) and [(COD)IrCl]2 (3.4 mg, 0.0050 mmol) as catalyst was conducted at room temperature for 2 h. 1H NMR analysis of the crude reaction mixture indicated that the ratio of regioisomers was greater than 99/1. The mixture was then purified by flash column chromatography on silica gel (1.5% ethyl acetate in hexanes) to give 81% yield. HPLC analysis indicated that the enantiomeric excess of the product was 97% [Diacel Chiralcel® OD-H (0.46 cm×25 cm); hexanes/2-propanol=99.75/0.25; flow rate=0.6 mL/min; detection wavelength=254 nm; TR=19.1 (major) min., 20.3 min. (minor)]. [α]D20=−12.0 (c 2.10, CHCl3); 1H NMR (400.13 MHz, C6D6) δ 7.44-7.24 (m, 5H), 7.20-7.10 (m, 2H), 6.69 (t, J=7.2 Hz, 1H), 6.60 (d, J=8.0 Hz, 2H), 6.04 (ddd, J=16.8, 10.4, 6.4 Hz, 1H), 5.28 (dt, J=17.2, 1.2 Hz, 1H), 5.22 (dt, J=10.0, 1.2 Hz, 1H), 4.94 (t, J=4.4 Hz, 1H), 4.04 (br s, 1H). 13C NMR (100.5 MHz, C6D6) δ .61.1 (s, CH), 114.2 (s, CH═CH2), 115.9 (s, CH═CH2), 118.2, 127.7, 127.8, 129.1, 129.6, 139.6 (all s, Ar—CH), 142.4 (s, Ar—C), 147.8 (s, Ar—C).
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