Olefin metathesis catalysts and related methods

Details Olefin metathesis catalysts and related methods Olefin metathesis catalysts and related methods

2011-04-26

2011-04-26

Gonzalez, Porfirio Nazario (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C556S058000, C548S108000, C548S402000, C548S408000, C546S002000, C546S010000, C544S004000, C544S014000, C544S225000

Reexamination Certificate

active

07932397

ABSTRACT:
The present invention provides methods for the synthesis of catalysts and precursors thereof. Methods of the invention may comprise combining a catalyst precursor and at least one ligand to generate a catalytically active species, often under mild conditions and in high yields. In some cases, a wide variety of catalysts may be synthesized from a single catalyst precursor. Methods of the invention may also include the preparation of catalysts which, under reaction conditions known in the art, may have been difficult or impossible to prepare and/or isolate due to, for example, steric crowding at the metal center. The present invention also provides catalyst compositions, and precursors thereof, which may be useful in various chemical reactions including olefin metathesis. In some cases, methods of the invention may reduce the number of synthetic and purification steps required to produce catalysts and/or other reaction products, as well as reducing time, cost, and waste production.

REFERENCES:
patent: 5055628 (1991-10-01), Lin et al.
patent: 5889128 (1999-03-01), Schrock et al.
patent: 6121473 (2000-09-01), Schrock et al.
patent: 6271325 (2001-08-01), McConville et al.
patent: 6316555 (2001-11-01), Schrock et al.
patent: 6346652 (2002-02-01), Schrock et al.
patent: 6610806 (2003-08-01), Schrock et al.
patent: 6855839 (2005-02-01), McConville et al.
patent: 7135544 (2006-11-01), Schrock et al.
Schrock et al., Organometallics, vol. 9, No. 8, pp. 2262-2275 (1990).
Cantrell et al., Organometallics, vol. 19, pp. 3562-3568 (2000).
International Preliminary Report on Patentability from International Patent Application Serial No. PCT/US2007/024318, filed Nov. 21, 2007, mailed May 26, 2009.
Al Obaidi, N. et al., “Steric and Electronic Effects on the Chemistry of Molybdenum Octahedrally Co-ordinated by Six Nitrogen Atoms. The Molecular Structure of [Mo{HB(3,5-Me2C3N2H)3}(NO)(pyrollide)2],”J. Chem. Soc., Chem. Commun. 1984, 6990.
Ascenso, J. et al., “Synthesis and characterization of [W(NC4Me4)2CI2] and [W(NC4Me4)2(CH3)2], the first azametallocene tungsten complexes with pyrrolyl ligands. Electronic structure and bonding of tungsten bispyrrolyl complexes,”Inorg. Chem. Acta2003, 356, 249.
Blackwell, J. et al., “Enediynes via sequential acetylide reductive coupling and alkyne metathesis: Easy access to well-defined molybdenum initiators for alkyne metathesis,”Organometallics2003, 22, 3351-3353.
Blanc, F. et al., “Surface versus molecular siloxy ligands in well-defined olefin metathesis catalysis: [{(RO)3SiO}Mo(=NAr)(=CHtBu)(CH2tBu)],”Angew. Chem. Int. Ed. 2006, 45, 1216-1220.
Dias, A. et al., “Synthesis, characterisation, crystal structure, reactivity and bonding in titanium complexes containing 2,3,4,5-tetramethylpyrrolyl,”J. Chem. Soc., Dalton Trans. 1997, 1055.
Duarte, M. et al., “Chlorobis(dimethylamido)(η5-2,5-dimethylpyrrolyl)titanium(IV), [Ti(NMe2)2(DMP)CI],”Acta Cryst. C. 2005, 61, 104.
Feldman, J. et al.,Prog. Inorg. Chem. 1991, 39, 1.
Fürstner, A. et al., “Mo[N(t-Bu)(Ar)]3complexes as catalyst precursors: in situ activation and application to metathesis reactions of alkynes and diynes,”J. Am. Chem. Soc. 1999, 121, 9453-9454.
Fürstner, A. et al., “Alkyne metathesis: Development of a novel molybdenum-based catalyst system and its application to the total synthesis of Epothilone A and C,”Chem. Eur. J. 2001, 7(24), 5299-5317.
Kershner, D. et al., “η5-Heterocyclic Metal Carbonyls,”Coord. Chem. Rev. 1987, 79, 279.
Rhers, B. et al., “A well-defined, silica-supported tungsten imido alkylidene olefin metathesis catalyst,”Organometallics2006, 25, 3554-3557.
Schrock, R. et al., “Preparation of molybdenum and tungsten neopentylidyne complexes of the type M(CCMe3)(O2CR)3, their reactions with acetylenes, and the X-ray structure of theη3-cyclopropenyl complex W[C3(CMe3)Et2]O2CCH3)31,”Organometallics1986, 5, 25-33.
Schrock, R. et al., “Synthesis of Molybdenum Imido Alkylidene Complexes and Some Reactions Involving Acyclic Olefins,”J. Am. Chem. Soc. 1990, 112, 3875.
Schrock, R., “High oxidation state multiple metal-carbon bonds,”Chem. Rev. 2002, 102, 145-179.
Schrock, R. et al., “Molybdenum and tungsten imido alkylidene complexes as efficient olefin-metathesis catalysts,”Angew. Chem. Int. Ed. 2003, 42, 4592-4633.
Schrock, R. et al., “Molybdenum alkylidyne complexes that contain 3,3′-di-t-butyl-5,5′, 6,6′-tetramethyl-1, 1′—biphenyl-2,2′—diolate ([Biphen]2-) ligand,”J. Organomet. Chem. 2003, 684, 56-67.
Sinha, A. et al., “Diphenylamido precursors to bisalkoxide molybdenum olefin metathesis catalysts,”Organometallics2006, 25, 4621-4626.
Sinha, A. et al., “Reactions of M(N-2,6-i-Pr2C6H3)(CHR)(CH2R′)2(M = Mo, W) Complexes with Alcohols to Give Olefin Metathesis Catalysts of the Type M(N-2,6-i-Pr2C6H3)(CHR)(CH2R′)(OR″),”Organometallics2006, 25, 1412.
Tonzetich, Z. et al., “Reaction of Phosphoranes with Mo(N-2,6-i-Pr2C6H3)(CHCMe3)[OCMe(CF3)2]2: Synthesis and Reactivity of an Anionic Imido Alkylidyne Complex,”Organometallics2006, 25, 4301.
Tsai, Y. et al, “Facile synthesis of trialkoxymolybdenum(VI) alkylidyne complexes for alkyne metathesis,”Organometallics2000, 19, 5260-5262.
Zhang, W. et al., “A reductive recycle strategy for the facile synthesis of molybdenum(VI) alkylidyne catalysts for alkyne metathesis,”Chem. Commun. 2003, 832-833.
Blanc, Frederic et al., “Dramatic Improvements of Well-Defined Silica Supported Mo-Based Olefin Metathesis Catalysts by Tuning the N-Containing Ligands,”J. Am. Chem. Soc. 2007, 129(27), 8434-8435.
Blanc, Frederic et al., “Highly Active, Stable, and Selective Well-Defined Silica Supported Mo Imido Olefin Metathesis Catalysts,”J. Am. Chem. Soc. 2007, 129(17), 1044-1045.
Hock, Adam S. et al., “Dipyrrolyl Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts,”J. Am. Chem. Soc. 2006, 128(50), 16373-16375.
Kreickmann, T., et al., “Imido Alkylidene Bispyrrolyl Complexes of Tungsten,”Organometallics2007, 26, 5702-5711.
Singh, Rojendra et al., “Molybdenum Imido Alkylidene Metathesis Catalysts That Contain Electron-Withdrawing Biphenolates or Binaphtholates,”Organometallics2007, 26(10), 2528-2539.
Singh, Rojendra et al., “Synthesis of Monoalkoxide Monopyrrolyl Complexes Mo(NR)(CHR′)(OR″)(pyrrolyl): Enyne Metathesis with High Oxidation State Catalysts,”J. Am. Chem. Soc. 2007, 129(42), 12654-12655.
Sinha, Amritanshu, et al., “Diphenylamido Precursors to Bisalkoxide Molybdenum Olefin Catalysts,”Organometallics2006, 25(19), 4621-4626.
International Search Report and Written Opinion in PCT/US2007/024318, issued on May 7, 2008.
[No Author Listed] New catalysts promise faster, cleaner, and more efficient research platform. Science Daily. Nov. 16, 2008. 2 pages.
Aeilts et al., A readily available and user-friendly chrial catalyst for efficient enantioselective olefin metathesis. Angew Chem Int Ed. 2001;40(8):1452-6.
Agbossou et al., Synthesis and Reactivity of Chiral Rhenium Alcohol Complexes of the Formula [(η5-C5H5)Re(NO)(PPh3)(ROH)]⊕ BF4⊖ . Chem Berichte. 1990;123(6):1293-9.
Anderson et al., Kinetic selectivity of olefin metathesis catalysts bearing cyclic (alkyl)(amino)carbenes. Organometallics. 2008;27(4):563-6.
Bailey et al., Evaluation of molybdenum and tungsten metathesis catalysts for homogeneous tandem alkane metathesisorganometallics. 2009;28(1):355-60.
Bazan et al., Living ring-opening metathesis polymerization of 2,3-difunctionalized 7-oxanorbornenes and 7-oxanorbornadienes by Mo(CHCMe2R)(NC6H3-iso-Pr2-2,6)(O-tert-Bu)2 and Mo(CHCMe2R)(NC6H3-iso-Pr2-2,6)(OCMe2CF3)2. J Am Chem Soc. 1991;113(18):6899-907.
Bei et al., Highly efficient olefin-metathesis catalysts. Phar

Affiliated with

Also associated with

Rating

Olefin metathesis catalysts and related methods does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Olefin metathesis catalysts and related methods, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Olefin metathesis catalysts and related methods will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2710058