Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1987-11-05
1989-10-10
Schwartz, Richard A.
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
540479, 546 58, 546 75, 546149, 556136, 568633, 585360, 585361, C07D30793
Patent
active
048733490
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a method for the intramolecular oxidative biaryl coupling of precursor compounds containing two aromatic rings linked to each other via a hydrocarbon chain.
The invention also relates to a new organometallic catalyst for oxidative biaryl coupling and to new compounds having bridged biaryl structure, which could be produced by implementing the method of the invention.
A number of bridged biaryl alkaloids have already been synthesized by oxidative biaryl coupling. Thus, S. M. Kupchan et al. have used vanadium oxyfluoride as coupling agent [S. M. Kupchan, K. K. Chakravarti, M. Yokoryama, J. Pharm. Sci., 985 (1963); S. M. Kupchan, A. J. Liepa, V. Kamesvaran, R. F. Bryan, J. Am. Chem. Soc., 6861 (1973) and the references cited; S. M. Kupchan, O. P. Dhingra, C. K. Kim, V. Kamesvaran, J. Org. Chem., 252 (1978) and the references cited; S. M. Kupchan, C. K. Kim, J. Am. Chem. Soc., 5663 (1975) and the references cited].
Additionally, thallium (III) tris(trifluoroacetate) has also already been recommended a coupling agent, for example by A. McKillop et al. [A. McKillop, A. G. Turrell, E. C. Taylor, J. Org. Chem., 765 (1977)] and by Cambie et al. [R. C. Cambie, G. R. Clark, P. A. Craw, P. S. Rutledge, P. D. Woodgate, Aust. J. Chem., 1775 (1984)].
However, these previous techniques have a number of disadvantages. First of all, they do not enable clean reaction mixtures to be obtained at the end of the procedure; it is therefore not easy to separate therefrom the synthesized compound which can therefore be obtained only with very low yields. Furthermore, it should be added that the handling of thallium salts requires very high precautions and that their recovery from the reaction medium presents great practical problems.
Because of these major disadvantages, the scaling up of such synthetic methods to an industrial scale cannot be envisaged. Finally, it should be added that these synthetic methods of the prior art could only be implemented at temperatures well below 0.degree. C., which forms an obvious additional disadvantage.
The present invention is precisely aimed at overcoming all the disadvantages attached to the synthetic method of the known prior art.
The present invention relates to a method for the intramolecular oxidative biaryl coupling of precursor compounds containing two aromatic rings, which may be polycondensed and which may contain one or more hetero atoms such as oxygen or nitrogen, linked to each other via a straight-chain or branched, saturated or unsaturated hydrocarbon chain, which may optionally contain one or more hetero atoms such as oxygen and/or nitrogen, wherein the biaryl precursors are cyclized in the presence of ruthenium (IV) tetrakis(trifluoroacetate), especially produced in situ.
The invention also relates to new ruthenium (IV) tetrakis (trifluoroacetate) catalysts for intramolecular oxidative biaryl coupling.
Finally, the present invention also extends to new biaryl compounds which could be synthesized by implementing the coupling method according to the invention and which prove to have very useful antiviral properties, especially against herpesvirus. These new compounds may also form part of the composition of therapeutic preparations, especially of preparations for use by local application.
Other characteristics and advantages of the present invention will appear on reading the detailed description given below, especially referring to the particular examples of preparation given simply by way of illustration.
In a very general way, the process according to the invention relates to intramolecular oxidative biaryl coupling leading to compounds having a bridged biaryl structure, which are very diverse in nature. This coupling is carried out on precursors containing two aromatic rings linked to each other via a hydrocarbon chain. Each of the two aromatic rings, necessarily present in the structure of the precursors, may be either monocyclic or polycyclic; it may also contain one or more substituents and may contain one or more hetero atoms such as oxyge
REFERENCES:
Taafrout et al., Tetrahedron Letters, vol. 24, No. 29, 1983, "Neoisostegane, A New Bisbenzocyclooctadienol Actonic Lignand from Steganotaenia araliacea Hochst", pp. 2983-2986.
Hicks et al, Tetrahedron Letters, vol. 24, No. 29, 1983, "Neoisostegane, A New Bisbenzocyclooctadiene Lignan Lactone from Steganotaenia araliacea Hochst", pp. 2987-2990.
McKillop et al., Journal of Organic Chemistry, vol. 42, No. 4, 1977, pp. 764-765.
Chemical Abstracts, vol. 71, No. 4, Abstract No. 21783p, Jul. 28, 1969, pp. 288-289.
Landais Yannick
Robin Jean-Pierre
Northington Zinna
Schwartz Richard A.
Universite Du Maine (Le Mans)
LandOfFree
Ruthenium catalyst for biarylic coupling; new steganolides does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Ruthenium catalyst for biarylic coupling; new steganolides, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Ruthenium catalyst for biarylic coupling; new steganolides will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-1958529