Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2001-08-03
2003-05-13
Nazario-Gonzalez, Porfirio (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C544S178000, C548S490000, C549S462000, C556S028000, C560S024000, C502S154000, C502S155000
Reexamination Certificate
active
06562989
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to transition metal catalysts for aromatic or vinylic C—O, C—N, and C—C bond formation, and more particularly to transition metal catalysts for aromatic or vinylic C—O, C—N, and C—C bond formation that include ferrocenyl ligands and a transition metal atom such as platinum, palladium, or nickel. The present invention also relates to method of forming compounds containing aromatic C—O, C—N, and C—C bonds using the transition metal catalysts.
2. Brief Description of the Related Art
Mild, aromatic or vinylic substitution to form C—O, C—N, and C—C bonds is a difficult transformation. For reactions of unactivated aryl halides, direct, uncatalyzed substitutions and copper-mediated couplings typically require temperatures of 100° C. or greater (Bacon, R. G. R.; Rennison, S. C.
J. Chem. Soc.
(
C
) 1969, 312-315; Marcoux, J. F.; Doye, S.; Buchwald, S. L.
J. Amn. Chem. Soc.
1997, 119, 10539-10540; Kalinin, A. V.; Bower, J. F.; Riebel, P.; Snieckus, V.
J. Org. Chem.
1999, 64, 2986-2987).
Alternative approaches have suffered similar drawbacks and disadvantages. For example, diazotization and displacement with oxygen or nitrogen nucleophiles is generally limited in scope and uses stoichiometric amounts of copper in its mildest form (March, J. In
Advanced Organic Chemistry
John Wiley and Sons: New York, 1985; pp 601). Recently, palladium catalysts for the formation of diaryl and alkyl aryl ethers from unactivated aryl halides have been shown to be useful in these reactions (Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F.
J. Am. Chem. Soc.
1999, 121, 3224-3225). However, this system for C—O bond-formation as well as similar systems (Aranyos, A.; Old, D. W.; Kiyomori, A.; Wolfe, J. P.; Sadighi, J. P.; Buchwald, S. L.
J. Am. Chem. Soc.
1999, 121, 4369-4378) required temperatures similar to those for copper-mediated processes (Bacon, R. G. R.; Rennison, S. C.
J. Chem. Soc.
(
C
) 1969, 312-315; Marcoux, J. F.; Doye,. S.; Buchwald, S. L.
J. Am. Chem. Soc.
1997, 119, 10539-10540; Kalinin, A. V.; Bower, J. F.; Riebel, P.; Snieckus, V.
J. Org. Chem.
1999, 64, 2986-2987; Boger, D. L.; Yohannes, D.
J. Org. Chem.
1991, 56, 1763; Fagan, P. J.; Hauptman, E.; Shapiro, R.; Casalnuovo, A.
J. Am. Chem. Soc.
2000, 122, 5043-5051). In addition, several catalysts have been shown to induce aromatic C—N bond-formation from aryl halides and sulfonates. Yet, the termperatures, for general reactions remain high in many cases, and the selectivities for formation of the desired aniline derivative instead of the undesired arene or diarylamine are often lower than optimal for synthetic applications.(Wolfe, J. P.; Buchwald, S. L.
J. Org. Chem.
2000, 65, 1444; Wolfe, J. P.; Buchwald, S. L.
J. Org. Chem.
2000, 65, 1158; Huang, J.; Grassa, G.; Nolan, S. P.
Org. Lett.
1999, 1, 1307; Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M.
J. Org. Chem.
1999, 64, 5575; Stauffer, S. I.; Hauck, S. I.; Lee, S.; Stambuli, J.; Hartwig, J. F.
Org. Lett.
2000, 2, 1423) Finally, catalysts have been developed for aromatic or vinylic C—C bond formation, but again the conditions for these reactions are often harsh.(Suzuki, A.
J. Organomet. Chem.
1999, 576, 147; Buchwals, S. L.; Fox, J. M.
The Strem Chemiker,
2000, 18, 1; Zhang, C; Huang, J.; Trudell, M. L.; Nolan, S. P.
J. Org. Chem.
1999, 64, 3804; Beletskaya, I. P. Cheprakov, A. V.
Chem. Rev.
2000, 100, 3009; Littke, A. F.; Fu, G. C.
J. Org. Chem.
1999, 64, 10; Shaughnessy, K. H.; Hartwig, J. F.
J. Am. Chem. Soc.
1999, 121, 2123) In particular for each of these three classes of reactions, the bond-forming processes are especially difficult to conduct under mild conditions with high selectivity when using chloroarenes.
Unfortunately, reaction conditions such as those described above are quite harsh and require special equipment and techniques to accomplish even small scale syntheses. In addition, larger scale reactions of these reactions, such as those used in large-scale pharmaceutical manufacturing, are generally impractical and expensive due to these extreme reaction conditions. What is needed in the art is a catalytic method of aromatic or vinylic carbon-oxygen, carbon-nitrogen, and carbon-carbon bond formation that occurs under mild conditions (e.g., room temperature and atmospheric pressure) and that is easily scalable for large-scale synthesis, for example, in the pharmaceutical industry. The present invention is believed to be an answer to that need.
SUMMARY OF THE INVENTION
In one aspect, the present invention is directed to a transition metal catalyst, comprising a Group 8 metal and a ligand having the structure
wherein R, R′ and R″ are organic groups having 1-15 carbon atoms, n=1-5, and m=0-4.
In another aspect, the present invention is directed to a method of forming a compound having an aromatic or vinylic carbon-oxygen, carbon-nitrogen, or carbon-carbon bond, comprising the step of reacting a first substrate and a second substrate in the presence of a transition metal catalyst, wherein the first substrate comprises an aryl halide reagent or an aryl sufonate reagent, and the second substrate comprises an alcohol reagent, an alkoxide reagent, a silanol reagent, a siloxide reagent, an amine reagent, an organoboron reagent, an organozinc reagent, an organomagnesium reagent, a malonate reagent, a cyanoacetate reagent, or an olefinic reagent, and wherein the transition metal catalyst comprises a Group 8 metal and a ligand having the structure
wherein R and R′ are organic groups having 1-15 carbon atoms, and n=1-5; under reaction conditions effective to form the compound, wherein the compound has an aromatic carbon-oxygen, carbon-nitrogen, or carbon-carbon bond between the first substrate and the second substrate.
In yet another aspect, the present invention is directed to a method of forming a compound having an aromatic carbon-oxygen, carbon-nitrogen, or carbon-carbon bond, comprising the step of reacting a first substrate and a second substrate in the presence of a transition metal catalyst, wherein the first substrate comprises a selected aryl halide reagent or an aryl sufonate reagent and the second substrate is selected from the group consisting of NaO—C
6
H
4
—OMe, NaO-tBu, NaO—Si-(tBu)Me
2
, HO—C
6
H
4
—OMe, HO-tBu, HO—Si-(tBu)Me
2
, primary amines, secondary amines, alkyl amines, benzylic amines, aryl amines including morpholine, dibutylamine, aniline, n-butylamine, n-hexylamine, methylaniline, aminotoluene; organoboron reagents, organozinc reagents, organomagnesium reagents, indoles, ethyl cyanoacetate, diethyl malonate, methyl acrylate, and combinations thereof, and wherein the transition metal catalyst comprises a Group 8 metal selected from the group consisting of palladium, platinum, and nickel, and a ligand having the structure
in a solvent selected from the group consisting of aromatic hydrocarbons, chlorinated aromatic hydrocarbons, ethers, water, aliphatic alcohols, and combinations thereof, under reaction conditions effective to form the compound, wherein the compound has an aromatic carbon-oxygen, carbon-nitrogen, or carbon-carbon bond between the first substrate and the second substrate.
These and other aspects will become apparent upon reading the following detailed description of the invention.
DETAILED DESCRIPTION OF THE INVENTION
It now has been surprisingly found, in accordance with the present invention, that a solution is provided to the problem of providing a general and efficient catalytic method of aromatic or vinylic carbon-oxygen, carbon-nitrogen, and carbon-carbon bond formation between two substrates that occurs under mild conditions (e.g., room temperature and atmospheric pressure). The present inventors have solved this problem by utilizing a catalyst that includes a transition metal catalyst comprising a Group 8 metal and a substituted ferrocenylphosphineligand. The catalyst is useful in a general and efficient process of formation of
Hartwig John F.
Kataoka Noriyasu
Shelby Quinetta
Garabedian Todd E.
Nazario-Gonzalez Porfirio
Wiggin & Dana LLP
Yale University
LandOfFree
Catalyst for aromatic C—O, C—N, and C—C... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Catalyst for aromatic C—O, C—N, and C—C..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Catalyst for aromatic C—O, C—N, and C—C... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3082660