Synthesis of Primary Amines: First Homogeneously Catalyzed Reductive Amination with Ammonia

Organic Letters

Volumn 4, Issue 12, 2002, Pages 2055-2058

  Gross, Thoralf ^a   Seayad, Abdul Majeed ^a   Ahmad, Moballigh ^a   Beller, Matthias ^a  

^a UNIVERSITY OF ROSTOCK   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE;

EID: 0012975811     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0200605     Document Type: Article

References (22)

1. For general references, see: (a) March, J. Advanced Organic Chemistry, 4th ed.; Wiley: New York, 1992; p 768 and references therein. (b) Collman, J. P.; Trost, B. M.; Veroeven, T. R. In Comprehensive Organometallic Chemistry, Wilkinson, G., Stone, F. G. A., Eds.; Pergamon Press: Oxford, 1982; Vol. 8, p 892 and references therein. Müller, T. E.; Beller, M. Chem. Rev. 1998, 98, 675. Gibson, M. S. In The Chemistry of Amino Group; Patai, S., Ed.; Interscience: New York, 1968; p 61.
2. For general references, see: (a) March, J. Advanced Organic Chemistry, 4th ed.; Wiley: New York, 1992; p 768 and references therein. (b) Collman, J. P.; Trost, B. M.; Veroeven, T. R. In Comprehensive Organometallic Chemistry, Wilkinson, G., Stone, F. G. A., Eds.; Pergamon Press: Oxford, 1982; Vol. 8, p 892 and references therein. Müller, T. E.; Beller, M. Chem. Rev. 1998, 98, 675. Gibson, M. S. In The Chemistry of Amino Group; Patai, S., Ed.; Interscience: New York, 1968; p 61.
3. For general references, see: (a) March, J. Advanced Organic Chemistry, 4th ed.; Wiley: New York, 1992; p 768 and references therein. (b) Collman, J. P.; Trost, B. M.; Veroeven, T. R. In Comprehensive Organometallic Chemistry, Wilkinson, G., Stone, F. G. A., Eds.; Pergamon Press: Oxford, 1982; Vol. 8, p 892 and references therein. (c) Müller, T. E.; Beller, M. Chem. Rev. 1998, 98, 675. Gibson, M. S. In The Chemistry of Amino Group; Patai, S., Ed.; Interscience: New York, 1968; p 61.
4. For general references, see: (a) March, J. Advanced Organic Chemistry, 4th ed.; Wiley: New York, 1992; p 768 and references therein. (b) Collman, J. P.; Trost, B. M.; Veroeven, T. R. In Comprehensive Organometallic Chemistry, Wilkinson, G., Stone, F. G. A., Eds.; Pergamon Press: Oxford, 1982; Vol. 8, p 892 and references therein. Müller, T. E.; Beller, M. Chem. Rev. 1998, 98, 675. (d) Gibson, M. S. In The Chemistry of Amino Group; Patai, S., Ed.; Interscience: New York, 1968; p 61.
5. (a) Rylander, P. N. Catalytic Hydrogenation in Organic Synthesis, Academic Press: New York, 1979; p 165.
6. (b) Rylander, P. N. Hydrogenation over Platinum Metals; Academic Press: New York, 1967; p 292.
7. (c) Heinen, A. W.; Peters, J. A.; van Bekkum H. Eur. J. Org. Chem. 2000, 2501.
8. Tararov, V. I.; Kadyrov, R.; Riermeier, T. H.; Börner, A. Chem. Commun. 2000, 1867.
9. (a) Zimmermann, B.; Herwig, J.; Beller, M. Angew. Chem. 1999, 111, 2515; Angew. Chem., Int. Ed. 1999, 38, 2372.
10. (a) Zimmermann, B.; Herwig, J.; Beller, M. Angew. Chem. 1999, 111, 2515; Angew. Chem., Int. Ed. 1999, 38, 2372.
11. (b) Zimmermann, B.; Herwig, J.; Beller, M. In Catalysis of Organic Reactions; Herkes, F., Ed.; Marcel Dekker: 2000.
12. (c) Review: Eilbracht, P.; Bärfacker, L.; Buss, C.; Hollmann, C.; Kitsos-Rzychon, B. E.; Kranemann, C. L.; Rische, T.; Roggenbuck, R.; Schmidt, A. Chem. Rev. 1999, 99, 3329.
13. Tafesh, A.; Beller, M. Tetrahedron Lett. 1995, 36, 9305.
14. We have been informed that, parallel to our work, this goal has been achieved by R. Kadyrov (Degussa AG). Kadyrov, R.; Riermeier, T. H., manuscript in preparation.
15. (a) Togni, A.; Breutel, C.; Schnyder, A.; Spindler F.; Landert, H.; Tijani, A. J. Am. Chem. Soc. 1994, 116, 4062.
16. (b) Blaser, H.-U.; Buser, H. P.; Coers, K.; Hanreich, R.; Jalett, H.-P.; Jelsch, E.; Pugin, B.; Schneider, H.-D.; Spindler F.; Wegmann, A. Chimia 1999, 53, 275.
17. (c) Blaser, H.-U.; Buser, H. P.; Jalett, H.-P.; Pugin, B.; Spindler F. Synlett 1999, 867.
18. Herrmann, W. A.; Kohlpaintner, C. W. Angew. Chem. 1993, 105, 1588; Angew. Chem., Int. Ed. Engl. 1993, 32, 1524.
19. Herrmann, W. A.; Kohlpaintner, C. W. Angew. Chem. 1993, 105, 1588; Angew. Chem., Int. Ed. Engl. 1993, 32, 1524.
20. Satory, Y.; Makoto, H.; Yuzuru, T. Nippon Kagaku Kaishi 1998, 8, 525.
21. 2, and the reaction was carried out for 2 h at a temperature of 135°C (total pressure at 135°C was ca. 100 bar). After the reaction, the autoclave was cooled to rt and slowly depressurized. The organic layer was collected, and the aqueous phase was treated with NaOH (0.5 g) and extracted with THF (2 × 10 mL). Bis-(methoxyethyl) ether (5 mL) was added to the combined organic phases, and the mixture was analyzed by gas chromatography. All aldehydes as well as synthesized amines and corresponding alcohols are commercially available. Therefore, benzaldehyde and products were identified by comparison with authentic samples by GC (column: cross-linked 5% PH ME Siloxane, 30 m × 0.25 mm × 0.25 μm). In addition, all products were confirmed by GC-MS.
22. 3 (20 mL), and freshly distilled toluene (10 mL) were charged under an argon atmosphere into a 100 mL stainless steel Parr autoclave equipped with an overhead stirrer and temperature-controlled heating, and the reaction was carried out at 145°C and 65 bar of hydrogen for 10 h. After the reaction, the organic layer was collected; the aqueous layer was washed twice (5 mL) with toluene, and the combined organic layers were analyzed by GC (column: cross-linked 5% PH ME Siloxane, 30 m × 0.25 mm × 0.25 μm). The products were also confirmed by GC-MS.