반응 #42716

반응 방정식

benzylamine

methyl cinnamyl carbonate

aniline

methyl cinnamyl carbonate

→

(−)-1-(1-Phenyl-2-propenyl)phenylamine

수율 81.0%

용매

CHCl3

반응 조건

후처리

1. 1
   기타1H NMR analysis of the crude reaction mixture
2. 2
   기타The mixture was then purified by flash column chromatography on silica gel (1.5% ethyl acetate in hexanes)
3. 3
   기타to give 81% yield

실험 절차

By 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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