DOI: 10.1016/s0040-4039(97)01464-0. An Improved Method for the Palladium-Catalyzed Amination of Aryl Triflates

An Improved Method for the Palladium-Catalyzed Amination of Aryl Triflates

10.1016/s0040-4039(97)01464-0

Crossref journal-article

Elsevier BV

Tetrahedron Letters (78)

Bibliography

Ãhman, J., & Buchwald, S. L. (1997). An Improved Method for the Palladium-Catalyzed Amination of Aryl Triflates. Tetrahedron Letters, 38(36), 6363â6366.

Authors 2

Jens Åhman (first)
Stephen L Buchwald (additional)

References 11 Referenced 103

(a) Wolfe, J.P.; Buchwald, S.L. J. Org. Chem. 1997, 62, 1264–1267. (10.1021/jo961915s)
(b) Louie, J.; Driver, M.S.; Hamann, B.C.; Hartwig, J.F. J. Org. Chem. 1997, 62, 1268–1273. (10.1021/jo961930x)
Wolfe, J.P.; Buchwald, S.L. Tetrahedron Lett. 1997, preceding paper in this issue. (10.1016/S0040-4039(97)01463-9)
DPPF = 1,1′-bis(diphenylphophino)ferrocene, PPF-OMe = 1-[2-(Diphenylphosphino)ferrocenyl]ethyl methyl ether.
All products were characterized by NMR (1H, 13C) and IR. Combustion analyses were obtained for new compounds.
Prevously reported compounds: (a) N-(p-benzoylphenyl)pyrrolidine (entry 1).[1]a (b) N-(p-benzoylphenyl)morpholine (entry 2).[1]a (c) N-(p-cyanophenyl)morpholine (entry 3).[1]a (d) N-(4-acetylphenyl)-p-anisidine (entry 5): Itier, J.: Casadevall, A. Bull. Soc. Chim. Fr. 1969, 3523–3538. (e) N-(4-acetylphenyl)pyrrolidine (entry 6): Ibata, T.; Isogami, Y.; Toyoda, J. Bull. Chem. Soc. Jpn. 1991, 64, 42–49. (f) 4-(4-carbomethoxyphenyl)morpholine (entry 10).[2](g) N-(4-methoxyphenyl)morpholine (entry 11): Tuji, Y.; Huh, K.T.; Ohsugi, Y.; Watanabe, Y. J. Org. Chem. 1985, 50, 1365–1370. (h) N-(2,4-dimethylphenyl)benzylamine (entry 13).[1]a N-(2,4-dimethylphenyl)pyrrolidine (entry 14): Walkup, R.E.; Seareles, S., Jr. Tetrahedron 1985, 41, 101–106. (i) N-(2-carbomethoxymethylphenyl)-p-anisidine (entry 15).[2]
Representative procedure: An oven-dried Schlenk tube was charged with Cs2CO3 (456 mg, 1.4 mmol) in a nitrogen-filled dry box.[7]The tube was capped with a rubber septum, removed from the dry box, and charged with Pd(OAc)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%).[1]a, [8]
The Cs2CO3 was weighed out in a dry box for reasons of convenience. 4-Cyanophenyl triflate was coupled with morpholine to give a 77% yield of the corresponding aniline (entry 3) using Cs2CO3 stored in a desiccator and weighed in the air. Entries 13–15 were set up with Cs2CO3 weighed in the air.
Efficient stirring is important in order to ensure short reaction times and optimum yields.
We believe that the low yields are due to byproducts formed via enolization processes.
Attempts to couple 2-carbomethoxyphenyl triflate with alkyl amines, such as pyrrolidine and benzyl amine, gave only low yields of the desired aniline.

Dates

Type	When
Created	23 years, 1 month ago (July 25, 2002, 4:37 p.m.)
Deposited	6 years, 4 months ago (April 16, 2019, 10:20 a.m.)
Indexed	1 year, 1 month ago (July 4, 2024, 7:30 p.m.)
Issued	27 years, 11 months ago (Sept. 1, 1997)
Published	27 years, 11 months ago (Sept. 1, 1997)
Published Print	27 years, 11 months ago (Sept. 1, 1997)

Funders 0

None

BibTeX

@article{_hman_1997, title={An Improved Method for the Palladium-Catalyzed Amination of Aryl Triflates}, volume={38}, ISSN={0040-4039}, url={http://dx.doi.org/10.1016/s0040-4039(97)01464-0}, DOI={10.1016/s0040-4039(97)01464-0}, number={36}, journal={Tetrahedron Letters}, publisher={Elsevier BV}, author={Åhman, Jens and Buchwald, Stephen L}, year={1997}, month=sep, pages={6363–6366} }

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