The synthesis of a new palladacycle catalyst. Development of a high performance catalyst for Heck reactions

Tetrahedron Letters

Volumn 40, Issue 41, 1999, Pages 7379-7383

  Miyazaki, Futoshi ^a   Yamaguchi, Kentaro ^b   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b CHIBA UNIVERSITY   (Japan)

Author keywords

Heck reactions; Pd catalysts

Indexed keywords

ALKENE; HALOGENATED HYDROCARBON; PALLADIUM COMPLEX;

ARTICLE; CATALYST; CHEMICAL REACTION KINETICS; SYNTHESIS;

EID: 0033536614     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01514-2     Document Type: Article

References (12)

1. 1. Herrmann, W. A.; Brossmer, C.; Reisinger, C.-P.; Riermeier, T. H.; Öfele, K.; Beller, M. Chem. Eur. J. 1997, 3, 1357.
2. 2. Ohff, M.; Ohff, A.; van der Boom, M. E.; Milstein, D. J. Am. Chem. Soc. 1997, 119, 11687.
3. 3. Shaw, B. L.; Perera, S. D.; Staley, E. A. Chem. Commun. 1998, 1361.
4. 4. Albisson, D. A.; Bedford, R. B.; Scully, P. N. Tetrahedron Lett. 1998, 39, 9793.
5. 5. Ohff, M.; Ohff, A.; Milstein, D. Chem. Commun. 1999, 357.
6. 2Pd, C; 45.63, H; 3.49. Found, C; 45.91, H; 3.26.
7. 7. The synthesis of 7 is as follows. To a solution of diethylphosphoramidous dichloride 6 (0.836 ml, 5.75 mmol) in THF (5.75 ml), a solution of triethylamine (1.6 ml, 11.5 mmol) and p-methoxyphenol (1.43 g, 11.5 mmol) in THF (5.75 ml) was added at -78°C. The resulting mixture was then warmed to room temperature and stirred overnight. The reaction mixture was filtered and the residue was rinsed with hexane. Concentration of the filtrate under reduced pressure gave the desired product 7 (2.00 g, quant.).
8. 3 (4 g, 3.86 mmol) were added and then the reaction mixture was stirred for 12 h at 23°C. The catalyst 5 was directly purified by silica gel column chromatography (first, hexane only; second, 3:1 hexane:ethyl acetate) to give the desired product (1.82 g, 26%) as a white powder.
9. 9. Holzapfel, C. W.; Bradley, D.; Williams, G. Tetrahedron 1995, 51, 8555.
10. 3) and concentrated, and the residual oil was purified by flash chromatography (silica gel, hexane:EtOAc (3:1)), furnishing the desired product (11 g, 53 mmol, 89%).
11. -1. The refinement (434 variables) based on F converged with R=0.050 and Rw=0.053 using 3301 unique reflections (I >2.00 δ(I)).
12. 12. We cannot obtain the good results when other substrates like bromobenzene, chlorobenzene and styrene are used.