Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts

a transition metal complex and catalyst technology, applied in the direction of group 3/13 element organic compounds, group 5/15 element organic compounds, hydrocarbon preparation catalysts, etc., can solve the problems of difficult substrates, low thermal stability of compounds, and few methods available for mild and selective synthesis of directly halogenated olefins

Inactive Publication Date: 2007-07-05
CALIFORNIA INST OF TECH
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  • Abstract
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  • Application Information

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Benefits of technology

[0016] The present invention is addressed to the aforementioned needs in the art, and provides a novel process for using certain Group 8 transition metal complexes to catalyze a variety of olefin metathesis reactions, primarily cross-metathesis reactions. The complexes used are metal carbenes comprised of a Group 8 transition metal, particularly ruthenium or osmium, which preferably, although not necessarily, contain an N-heterocyclic carbene ligand. Such complexes are highly active catalysts of olefin metathesis reactions, including the cross-metathesis reactions described in detail herein. In contrast to previous catalysts used in olefin cross-metathesis, the present complexes allow an olefinic reactan

Problems solved by technology

However, as has been recognized by those in the field, the compounds display low thermal stability, decomposing at relatively low temperatures.
These problems span a variety of reactions and starting materials.
However, elimination and/or loss of olefin stereochemical integrity are often competitive with product formation.
201), but are limited by the requirement of highly reactive functional groups in the substrates.
In these cases, the substrates are challenging because of the electron-withdrawing nature of the pendent halogens.
A particularly challenging situation arises when the olefin is directly halogenated, because the metathesis reaction will then involve a monohalo [M]=CXR or dihalo [M]=CX2 carbene complex as the propagating species (where X=hal

Method used

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  • Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts
  • Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts
  • Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts

Examples

Experimental program
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Effect test

example 1

Representative Procedure for Synthesis of Ruthenium Alkylidene Catalysts

Synthesis of RuCl2(═CH—CH═C(CH3)2)(IMesH2)(PCy3) (complex (2), Scheme 1)

[0138]

[0139] [Ru(COD)Cl2]n (300 mg, 1 mmol), IMesH2Cl (1.47 g, 4 mmol), tricyclohexylphosphine (300 mg, 1 mmol), and KN(SiMe3)2 (540 mg, 2.5 mmol) were weighed directly into a 600 mL Schlenk tube. The flask was evacuated and filled with dry argon (2×). Degassed benzene (300 mL) was added and the flask was pressurized to 30 psi with H2. The suspension was vigorously stirred for 12 hours at 90° C., yielding a bright yellow solution and white precipitate (1). After cooling the reaction to 5° C., propargyl chloride (0.3 mL, 4 mmol) was slowly added via syringe and the reaction mixture was allowed to warm to room temperature. The resulting brown benzene solution was washed with degassed 1 M HCl (2×), degassed brine (2×), filtered through Celite and concentrated in vacuo to afford compound (2) as a brown solid in 90% yield (95% purity). The brow...

example 2

Synthesis of RuCl2(═CH—CH═C(CH3)2)(IMesH2)(PPh3) (complex (4), Scheme 2)

[0141]

[0142] The procedure of Example 2 was employed using [Ru(COD)Cl2]11 (300 mg, 1 mmol), IMesH2Cl (0.74 g, 2 mmol), triphenylphosphine (280 mg, 1 mmol), and KN(SiMe3)2 (380 mg, 1.9 mmol), giving 550 mg (68%) of complex (3). 31P NMR (CD2Cl2): δ 24.0. 1H NMR (CD2Cl2): δ 18.49 (d, J=11.1 Hz, 1H).

example 3

Synthesis of RuCl2(═CH—CH-Ph)(IMesH2)(PCy3) (complex (5), Scheme 3)

[0143]

[0144] RuCl2(═CHPh)(PCy3), (phenylmethylene-bis(tricyclohexylphosphine) ruthenium dichloride, “catalyst (1)”) (6.00 g, 7.29 mmol, 1.0 eq.), IMesH2 HCl salt prepared above (2 eq.), and potassium t-butoxide (2 eq.) were placed in a Schlenk flask. 60 mL of anhydrous degassed hexanes (Aldrich SureSeal bottle) were added. A vacuum was applied to further degas the reaction mixture, which was then heated to 60° C. for 24 hours. The suspension changed color from purple to orange-brown over the reaction time. After approximately 24 hr, the mixture was cooled to room temperature, and an excess of 1:1 isopropanol:water (180 mL) was added. The mixture was stirred rapidly in air for 30 min., then filtered using a medium porosity frit, and washed with isopropanol-water (3×100 mL) and hexanes (3×100 mL). The solids were dried in in vacuo, and the yield was approximately 75%. 1H NMR (CD2Cl2, 400 MHz) δ 19.16 (s, 1H), 7.37-7.0...

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Abstract

The invention pertains to the use of Group 8 transition metal carbene complexes as catalysts for olefin cross-metathesis reactions. In particular, ruthenium and osmium alkylidene complexes substituted with an N-heterocyclic carbene ligand are used to catalyze cross-metathesis reactions to provide a variety of substituted and functionalized olefins, including phosphonate-substituted olefins, directly halogenated olefins, 1,1,2-trisubstituted olefins, and quaternary allylic olefins. The invention further provides a method for creating functional diversity using the aforementioned complexes to catalyze cross-metathesis reactions of a first olefinic reactant, which may or may not be substituted with a functional group, with each of a plurality of different olefinic reactants, which may or may not be substituted with functional groups, to give a plurality of structurally distinct olefinic products. The methodology of the invention is also useful in facilitating the stereoselective synthesis of 1,2-disubstituted olefins in the cis configuration.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a divisional of U.S. patent application Ser. No. 10 / 114,418. This application also claims priority under 35 U.S.C. §119(e)(1) to the following provisional U.S. patent applications: Ser. No. 60 / 280,590, filed Mar. 30, 2001; Ser. No. 60 / 280,462, filed Mar. 30, 2001; Ser. No. 60 / 284,213, filed Apr. 16, 2001; Ser. No. 60 / 285,597, filed Apr. 20, 2001; and Ser. No. 60 / 340,588, filed Dec. 14, 2001. The aforementioned applications are incorporated by reference in their entireties.ACKNOWLEDGEMENT OF GOVERNMENT SUPPORT [0002] This invention was developed with U.S. Government support under grant numbers 2 ROT GM31332 and 3 RO1 GM31332-16 awarded by the National Institutes of Health, and under grant number CHE 9809856 awarded by the National Science Foundation. The Government has certain rights in the invention.TECHNICAL FIELD [0003] This invention relates generally to a method for carrying out an olefin metathesis reaction usin...

Claims

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Application Information

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IPC IPC(8): C07F9/02C07F5/02C07F7/00C07C31/34C07C205/02C07C319/02C07C6/02C07C6/04C07C6/06C07C17/275C07C29/40C07C45/69C07C67/293C07C67/343C07C205/06C07C319/20C07C321/14C07D263/14C07D317/12C07D317/20C07D317/24C07F7/18C07F7/22C07F7/30C07F9/40C07F15/00
CPCC07C6/04C07F9/40C07C29/40C07C45/69C07C67/293C07C67/343C07C67/475C07C319/20C07C2101/14C07C2101/16C07C2103/74C07C2531/22C07D263/14C07D317/12C07D317/20C07D317/24C07F7/1892C07F9/4015C07F15/0046C07C17/275C07C67/297C07C41/14C07C29/46C07C201/12C07C25/13C07C47/21C07C69/007C07C69/78C07C69/732C07C69/56C07C321/14C07C69/16C07C69/533C07C69/145C07C69/157C07C69/18C07C205/06C07C2601/14C07C2601/16C07C2603/74C07C33/483
Inventor GRUBBS, ROBERT H.CHATTERJEE, ARNAB K.CHOI, TAE-LIMGODBERG, STEVEN D.LOVE, JENNIFER A.MORGAN, JOHN P.SANDERS, DANIEL P.SCHOLL, MATTHIASTOSTE, F. DEANTRNKA, TINA M.
Owner CALIFORNIA INST OF TECH
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