Benzoic Acid → (+/-)-(4-Isopropylphenyl){1-[4-(trifluoromethyl)phenyl]but-3-en-1-yl}amine

HRID 1869736Notes

Reaction equation

HRID 1869736 reaction equation
[C:1](O)(=O)[C:2]1C=CC=C[CH:3]=1.[F:10][C:11]([F:21])([F:20])[C:12]1[CH:19]=[CH:18][C:15]([CH:16]=O)=[CH:14][CH:13]=1.[CH:22]([C:25]1[CH:31]=[CH:30][C:28]([NH2:29])=[CH:27][CH:26]=1)([CH3:24])[CH3:23].C([Sn](CCCC)(CCCC)CCCC)C=C>CC#N.[O-]S(C(F)(F)F)(=O)=O.[La+3].[O-]S(C(F)(F)F)(=O)=O.[O-]S(C(F)(F)F)(=O)=O>[CH:22]([C:25]1[CH:31]=[CH:30][C:28]([NH:29][CH:16]([C:15]2[CH:18]=[CH:19][C:12]([C:11]([F:21])([F:20])[F:10])=[CH:13][CH:14]=2)[CH2:3][CH:2]=[CH2:1])=[CH:27][CH:26]=1)([CH3:24])[CH3:23]

Participants

7

Reactant 4

HCID 243Benzoic AcidHCID 74644-IsopropylanilineHCID 679964-(Trifluoromethyl)benzaldehydeHCID 90628Allyltributylstannane

Product 1

HCID 68420155(+/-)-(4-Isopropylphenyl){1-[4-(trifluoromethyl)phenyl]but-3-en-1-yl}amineYield 90%

Reagents, catalysts & solvents 2

HCID 2733938Lanthanum tris(trifluoromethanesulfonate)CatalystHCID 6342AcetonitrileSolvent

Procedure

Lanthanum triflate (0.141 g, 0.24 mmol, 2 mol %) and benzoic acid (1.49 g, 12.2 mmol) were dissolved in CH3CN (20 ml) and the suspension was stirred under nitrogen until dissolved. 4-(Trifluoromethyl)benzaldehyde (2.12 g, 12.2 mmol) was added followed by 4-isopropylaniline (1.65 g). Allyl(tributyl)stannane (4.54 ml, 14.6 mmol) was then added and the mixture was stirred at room temperature overnight. The mixture was then quenched with NaOH (2M, 20 ml) and extracted into DCM (3×100 ml). The combined extracts were dried (MgSO4) and the solvent was removed in vacuo to yield the crude homoallylic amine product. This was purified by chromatography on silica using 10-30% ether in hexane as eluant to yield the product as a colourless oil (3.65 g, 90%). 1H NMR (500 MHz, CDCl3) δ: 1.16 (6H, dd, J 1.3, 6.9), 2.42-2.48 (1H, m), 2.56-2.62 (1H, m), 2.71-2.79 (1H, qn, J 6.7), 4.07 (1H, s), 4.38 (1H, dd, J 4.9, 8.1), 5.18 (2H, m), 5.69-5.77 (1H, m), 6.40 (2H, d, J 8.4), 6.95 (2H, d, J 8.5), 7.49 (2H, d, J 8.1), 7.57 (2H, d, J 8.1); M/Z (ES+) 334 (MH+).

Workup

  1. dissolutionuntil dissolved
  2. stirringthe mixture was stirred at room temperature overnight
  3. customThe mixture was then quenched with NaOH (2M, 20 ml)
  4. extractionextracted into DCM (3×100 ml)
  5. dry with materialThe combined extracts were dried (MgSO4)
  6. customthe solvent was removed in vacuo
  7. customto yield the crude homoallylic amine product
  8. customThis was purified by chromatography on silica using 10-30% ether in hexane as eluant

Sources & evidence

ORD record
ord-ce6a3d520f4e41de8365a2b067c590ce
Source dataset
uspto-grants-2009_12
Patent number
US07638629B2

Reaction notes

Loading…