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Selective ring-opening cross-metathesis of cycloulefins

A cross-replacement and cyclic olefin technology, which is used in the production of hydrocarbons by metathesis reaction, the preparation of organic compounds, and compounds containing elements of Group 8/9/10/18 of the periodic table, etc., and can solve problems such as variation.

Inactive Publication Date: 2004-07-14
CALIFORNIA INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0015] Both systems typically use steric congestion to worsen ROMP relative to ROCM, imposing severe constraints on the backbone ring-opening of this synthetic approach

Method used

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  • Selective ring-opening cross-metathesis of cycloulefins
  • Selective ring-opening cross-metathesis of cycloulefins
  • Selective ring-opening cross-metathesis of cycloulefins

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0180] Synthesis of RuCl 2 (=CH-CH=C(CH 3 ) 2 ) (IMesH 2 )(PCy 3 ) (complex (2), route 1):

[0181]

[0182]

[0183] Pathway 1

[0184] Weigh directly into the main 600mL Schlenk tube and add [Ru(COD)Cl 2 ] n (300mg, 1mmol), IMesH 2 Cl (1.47g, 4mmol), tricyclohexylphosphine (300mg, 1mmol) and KN (SiMe 3 ) 2 (540 mg, 2.5 mmol). The flask was evacuated and filled with dry argon (2x). Degassed benzene (300 mL) was added and the flask was pressurized to 30 psi with H2. The suspension was stirred vigorously at 90°C for 12 hours, resulting in a pale yellow solution and a white deposit (1). After cooling the reaction to 5 °C, propargyl chloride (0.3 mL, 4 mmol) was added slowly via syringe and the reaction mixture was warmed to room temperature. The resulting brown benzene solution was washed with degassed 1M HCl (2x) and degassed brine (2x), filtered through celite, and concentrated in vacuo to afford compound (2) as a brown solid in 90% yield ( ~95% purity). ...

Embodiment 2

[0187] Synthesis of RuCl 2 (=CH-CH=C(CH 3 ) 2 ) (IMesH 2 ) (PPh 3 ) (complex (4), pathway 2):

[0188]

[0189]

[0190] Path 2

[0191] Using [Ru(COD)Cl 2 ] n (300mg, 1mmol), IMesH 2 Cl (0.74g, 2mmol), triphenylphosphine (280mg, 1mmol) and KN (SiMe 3 ) 2 (380 mg, 1.9 mmol) The procedure described in Example 1 was followed to form 550 mg (68%) of complex (4). 31 PNMR (CD 2 Cl 2 ): δ24.0. 1 H NMR (CD 2 Cl 2 ): δ 18.49 (d, J=11.1 Hz, 1H).

Embodiment 3

[0193] Synthesis of RuCl 2 (=CH-CH-Ph)(IMesH 2 )(PCy 3 ) (complex (5), pathway 3):

[0194]

[0195] Path 3

[0196] RuCl 2 (=CHPh)(PCy 3 ) s (Phenylmethylene-bis(tricyclohexylphosphine)ruthenium dichloride, "Catalyst (I)") (6.00 g, 7.29 mmol, 1.0 equiv), IMesH prepared above 2 • HCl salt (2 equiv) and potassium tert-butoxide (2 equiv) were added to the Schlenk flask. Add 60 mL of degassed anhydrous hexane (Aldrich SureSeal bottle). The reaction mixture was further degassed by evacuation and then heated to 60 °C for 24 hours. During the reaction time, the color of the suspension changed from purple to orange-brown. After about 24 hours, the mixture was cooled to room temperature and excess 1:1 isopropanol:water (180 mL) was added. The mixture was stirred rapidly for 30 minutes in air. It was then filtered using a medium porosity sintered glass filter-through bead and washed with isopropanol-water (3 x 100 mL) and hexane (3 x 100 mL). The solid was dried in vacuo...

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Abstract

A catalytic method is provided for a ring-opening cross-metathesis reaction between a cycloolefinic substrate and a second olefinic reactant, wherein the catalyst used is a transition metal alkylidene complex substituted with an N-heterocyclic carbene ligand. The substrates are selected so that the rate of the cross-metathesis reaction of the second olefinic reactant, kCM, is greater than or equal to the rate of the ring-opening metathesis reaction, kRo. In this way, the predominant ROCM product is a monomer, dimer, and / or oligomer, but not a polymer. The invention additionally provides for selective production of an end-differentiated olefinic product, using trisubstituted cycloolefins as substrates and / or a subsequent cross-metathesis reaction following an initial ROCM step. The cycloolefinic substrates include low-strain olefins such as cyclohexene as well as higher strain olefins such as cyclooctene.

Description

technical field [0001] The invention relates to a method for carrying out olefin metathesis reaction using a group 8 transition metal complex as a catalyst. More particularly, the present invention relates to a method for ring-opening cross-metathesis ("ROCM") reactions using the catalysts described above, wherein the cyclic olefin and the second olefin reactant are selected with reference to their relative reactivity in the ROCM reaction. Also provided are methods of catalyzing regioselective ROCM reactions and ROCM reactions involving at least one functionalized olefinic reactant. Background of the invention [0002] The operational flexibility of the described olefin metathesis reactions allows for the efficient preparation of highly functionalized unsaturated polymers and small molecules. Grubbs et al. (1998) Tetrahedron 54, 4413-4450; Randall et al. (1998) J. Mol. Cat. A-Chem. 133, 29-40; Trnka and Grubbs (2001) Acc. Chem. Res. 34, 18 -29. Many synthesis-related appl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D233/02B01J31/22B01J31/24C07B61/00C07C6/06C07C45/69C07C47/21C07C49/203C07C51/353C07C57/13C07C67/347C07C69/587C07C69/602C07C69/74C07F15/00C07F19/00
CPCB01J31/18C07C67/343C07C45/68C07C67/475B01J31/2404C07C6/06B01J2531/80B01J2231/543B01J31/2273B01J31/24C07C51/353B01J31/2226C07C2531/22B01J2531/821B01J2540/32C07C47/21C07C49/203C07C57/13C07C69/587C07C69/757C07C69/74C07C69/602
Inventor J·P·摩根C·莫里尔R·H·格鲁布斯崔太林
Owner CALIFORNIA INST OF TECH
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