Organic compounds -- part of the class 532-570 series – Organic compounds – Four or more ring nitrogens in the bicyclo ring system
Patent
1995-04-24
1996-08-27
Shah, Mukund J.
Organic compounds -- part of the class 532-570 series
Organic compounds
Four or more ring nitrogens in the bicyclo ring system
544333, 544334, 544335, 544409, 544316, 544224, 544405, 544315, 544242, 544410, 544360, 544364, 544395, 544403, 546339, 546345, 546302, 546303, 546261, 546239, 546259, 5462687, 546286, 546290, 546346, 546192, 5462697, 546193, 546194, 558357, 560102, 564181, 568437, 568642, 570143, 570182, 570190, 548239, C07D21326, C07D23930, C07D40104, C07D40304
Patent
active
055502369
DESCRIPTION:
BRIEF SUMMARY
The invention relates to a process for preparing polycyclic aromatic compounds by cross-coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates catalyzed by metallic palladium, if desired applied to a support material.
The palladium-catalyzed cross-coupling reaction of terminal alkynes and organometallic alkyl, alkenyl, allyl or aryl compounds with alkyl, alkenyl, allyl or aryl halides or sulfonates has been utilized to an increasing extent in many areas of organic synthesis for some years (see, for example B. M. Trost, T. R. Verhoeven in: Comprehensive Organometallic Chemistry Volume 8, p. 779 ff., Pergamon Press, Oxford 19 . . . ).
The cross-coupling of metallated aryls with aromatic halides has been carried out, for example, using Grignard and organolithium reagents (see, for example, J.-F. Fauvarque and A. Jutard, Bull. Chim. Soc. Fr., 1976, 765, A. Sekiya and N. Ishikawa, J. Organomet. Chem., 1976, 118, 349, A. Sekija and N. Ishikawa, J. Organomet. Chem., 1977, 125, 281, M. Yamamura, I. Moritani and S. I. Murahashi, J. Organomet. Chem., 1975, 91, C39, S. I. Murahashi, M. Yamamura, K. Yanagiswa, N. Mira and K. Kondo, J. Org. Chem., 1979, 44, 2408, A. Minato, K. Tamao, T. Hayashi, K. Suzuki and M. Kumada, Tetrahedron Lett., 1980, 845.), organozinc reagents (for example, E. Negishi et al. J. Org. Chem. 42 (1977) 1822. ) and organotin reagents (for example, M. Kosogi et al., Chem. Lett. 1977, 301.).
Aromatic boron compounds too, such as boronic acids and their derivatives or boranes, have already been used for coupling with aromatic halogen compounds or perfluoroalkylsulfonates (see, for example, B. N. Miyaura, T. Yanagi, A. Suzuki in Synthetic Communications 11 (1981), p. 513 ff.; M. J. Sharp, W. Cheng, V. Snieckus in Tetrahedron Letters 28 (1987), p. 5093 ff.; G. W. Gray in J. Chem. Soc. Perkin Trans II, 1989, p. 2041 ff. and Mol. Cryst, Sig. Cryst, 172 (1989), p. 165 ff., 204 (1991), p. 43 ff and p. 91 ff.; EP 0 449 015; WO 89/12039; WO 89/03821; EP 0 354 434).
All these processes are homogeneously catalyzed processes using Pd(0) complexes, in particular tetrakis(triphenylphosphine)palladium(0).
However, the disadvantage of these processes is clearly in the high catalyst costs which make difficult the economical transfer of the processes to a larger production scale (kg, t). The homogeneous reaction procedure furthermore makes difficult an efficient regeneration of the palladium catalyst and can easily lead to contamination of the waste formed in the reaction with palladium.
For this reason, processes have been developed which circumvent these problems by heterogeneous use of the catalyst. EP-A-0 152 450 describes the coupling of Grignard reagents under heterogeneous Pd(0) catalysis. However, owing to the high reactivity of the organomagnesium component, the selection of starting materials for this process is severely limited. The German Patent 3 930 663 describes a process for preparing liquid-crystalline compounds in which halides and organometallic compounds, including boronic acids, are reacted in inert solvents using metallic palladium, if desired applied to a support material, as catalyst, if desired in the presence of a metal alkoxide. Although this procedure can substantially reduce the catalyst costs and the palladium can easily be regenerated after the reactions are complete, this process often gives the desired coupling product in only unsatisfactory yields.
It is therefore an object of the present invention to find a process for coupling aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates, which process does not have the disadvantages described for the previous processes.
It has surprisingly been found that in the reaction of aromatic boronic acids with aromatic halogen compounds or perfluoroalkylsulfonates in the presence of a base and catalytic amounts of metallic palladium, if desired applied to a support material, excellent yields of polycyclic aromatic compounds can be obtained by addition of catalytic amounts of a liga
REFERENCES:
patent: 5254776 (1993-10-01), Lang et al.
Ali, Naji M., et al., "Palladium-Catalysed Cross-Coupling Reactions of Arylboronic Acids with .pi.-Deficient Heteroaryl Chlorides.sup.+1 " Tetrahedron, 48, No. 37, pp. 8117-8126, 1992. Month of publication not provided.
Manero Javier
Schlosser Hubert
Wingen Rainer
Hoechst Aktiengesellschaft
Shah Mukund J.
Wong King Lit
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