Aniline → (-)-1-(1-Phenyl-2-propenyl)phenylamine

HRID 14438Notes

Reaction equation

HRID 14438 reaction equation
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]=1

Participants

6

Reactant 3

HCID 6115AnilineHCID 7504BenzylamineHCID 54135828Methyl 3-phenylprop-2-en-1-yl carbonate2×

Product 1

HCID 68584977(-)-1-(1-Phenyl-2-propenyl)phenylamineYield 81%

Reagents, catalysts & solvents 2

HCID 178424610HCID 178424610, compoundCatalystHCID 6212ChloroformSolvent

Procedure

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).

Workup

  1. custom1H NMR analysis of the crude reaction mixture
  2. customThe mixture was then purified by flash column chromatography on silica gel (1.5% ethyl acetate in hexanes)
  3. customto give 81% yield

Sources & evidence

ORD record
ord-b3a8d0645afe485d9858b96a25151905
Source dataset
uspto-grants-2010_06
Patent number
US07732365B2

Reaction notes

Loading…