p-Toluenesulfonic acid → N-(cyclopropylmethyl)-1-phenylprop-2-en-1-amine

HRID 1392081Notes

Reaction equation

C(=O)(OC)O[CH2:3]/[CH:4]=[CH:5]/[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[NH2:15][CH2:16][CH:17]1[CH2:19][CH2:18]1.P(OC1C=CC=CC=1)(OC1C=CC=CC=1)OC1C=CC=CC=1.CC1C=CC(S(O)(=O)=O)=CC=1>CCO>[CH:17]1([CH2:16][NH:15][CH:5]([C:6]2[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=2)[CH:4]=[CH2:3])[CH2:19][CH2:18]1

Participants

Conditions

Temperature: 85 °C

Procedure

To a solution of (E)-cinnamyl methyl carbonate (0.73 g) in EtOH (8 mL) at RT under N2 was added (aminomethyl)cyclopropane (1 mL), triphenyl phosphite (0.096 g) and [Ir(COD)Cl]2 (0.051 g). The reaction mixture was stirred at 85° C. overnight, then cooled to RT. MP-TsOH resin (1.3 mmol/g, 9 g) and EtOH (30 mL) were added to the reaction and the resulting mixture stirred for 2 hr. The resin was filtered from the reaction mixture and thoroughly washed with EtOH. The isolated resin was then washed separately with ammonia (7 N in MeOH) and the filtrate was concentrated to an oil. The crude material was purified via column chromatography (10% then 15% EtOAc/hexanes) to give the desired product (0.13 g, 18%). 1H NMR (300 MHz, CDCl3) δ 0.045-0.092 (m, 2H), 0.42-0.49 (m, 2H), 0.92-1.02 (m, 1H), 2.33 (dd, 1H), 2.47 (dd, 1H), 4.21 (d, 1H), 5.08 (d, 1H), 5.19 (d, 1H), 5.88-5.99 (m, 1H), 7.23(m, 5H). MS APCI, m/z=188 (M+1). LC/MS 1.25 min., Method A.

Workup

temperaturecooled to RT
stirringthe resulting mixture stirred for 2 hr
filtrationThe resin was filtered from the reaction mixture
washthoroughly washed with EtOH
washThe isolated resin was then washed separately with ammonia (7 N in MeOH)
concentrationthe filtrate was concentrated to an oil
customThe crude material was purified via column chromatography (10%

Sources & evidence

ORD record: ord-d996601c35f84808bed85d2f69186a66
Source dataset: uspto-grants-2008_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07342007B2

Reaction notes

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