An improved method for the palladium-catalyzed amination of aryl triflates

Tetrahedron Letters

Volumn 38, Issue 36, 1997, Pages 6363-6366

  Åhman, Jens ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; ANILINE DERIVATIVE; MORPHOLINE DERIVATIVE; PYRROLIDINE DERIVATIVE;

AMINATION; ARTICLE; DRUG SYNTHESIS; IN VITRO STUDY; METHODOLOGY; REACTION ANALYSIS;

EID: 0030748897     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01464-0     Document Type: Article

References (17)

1. (a) Wolfe, J. P.; Buchwald, S. L. J. Org. Chem. 1997, 62, 1264-1267.
2. (b) Louie, J.; Driver, M. S.; Hamann, B. C.; Hartwig, J. F. J. Org. Chem. 1997, 62, 1268-1273.
3. Wolfe, J. P.; Buchwald, S. L. Tetrahedron Lett. 1997, preceding paper in this issue.
4. DPPF= 1,1′-bis(diphenylphophino)ferrocene, PPF-OMe = 1-[2-(Diphenylphosphino)ferrocenyl]ethyl methyl ether.
5. 13C) and IR. Combustion analyses were obtained for new compounds.
6. 2
7. 2
8. 2
9. 2
10. 2
11. 2
12. 2
13. 2 (6.7 mg, 0.03 mmol) and BINAP (28.2 mg, 0.045 mmol). The tube was flushed with Ar for 5 min, then a solution of 4-cyanophenyl triflate (251 mg, 1.0 mmol) and morpholine (105 μl, 1.2 mmol) in toluene (2 mL) was added via cannula and the resulting mixture was first stirred under Ar at room temperature for 30 min and then at 80°C for 16 h. The reaction mixture was allowed to cool to room temperature, diluted with ether (15 mL) and filtered through a pad of Celite and the filter cake was washed with ether (3 × 10 mL). Concentration and flash chromatography on silica gel afforded N-(p-cyanophenyl) morpholine (164 mg, 87%).1a, 8
14. 3 weighed in the air.
15. Efficient stirring is important in order to ensure short reaction times and optimum yields.
16. We believe that the low yields are due to byproducts formed via enolization processes.
17. Attempts to couple 2-carbomethoxyphenyl triflate with alkyl amines, such as pyrrolidine and benzyl amine, gave only low yields of the desired aniline.