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Ligands for metals and improved metal-catalyzed processes based thereon

A ligand and alkyl technology, applied in chemical instruments and methods, preparation of carbon-based compounds, compounds of Group 5/15 elements of the periodic table, etc., can solve problems such as high temperature, low product yield, long reaction time, etc.

Active Publication Date: 2006-03-08
MASSACHUSETTS INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Bromides are often acceptable substrates, but generally require higher temperatures, longer reaction times, and lower product yields

Method used

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  • Ligands for metals and improved metal-catalyzed processes based thereon
  • Ligands for metals and improved metal-catalyzed processes based thereon
  • Ligands for metals and improved metal-catalyzed processes based thereon

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0655] Highly active catalysts for palladium-catalyzed cross-coupling reactions: Suzuki coupling and amination of inactive aryl chlorides at room temperature

[0656] A highly active palladium catalyst has been developed using the chelating aminophosphine ligand 1-(N,N-dimethylamino)-1'-(dicyclohexylphosphino)biphenyl (2). The catalyst is effective for the cross-coupling of aryl chlorides with amines, boronic acids and keto enolates. The ample reactivity of this system is suitable for room-temperature amination of aryl bromides and electron-deficient aryl chlorides, as well as facilitating room-temperature Suzuki coupling reactions of electron-rich and electron-deficient aryl chlorides. The coordination of the amine moiety is the key to enhanced reactivity and catalyst stability of the system.

[0657] Palladium-catalyzed C–N bond-forming reactions have been implicated in versatile and efficient synthetic transformations. The use of palladium catalysts supported by bidentate...

Embodiment 2

[0813] Synthesis of N-(2,5-dimethylphenyl)-N-methylaniline.

[0814]

[0815] The dried test tube was purged with argon and filled with Pd 2 (dba) 3 (4.6 mg, 0.005 mmol, 1.0 mol% Pd), Ligand 2 [Example 1] (6.0 mg, 0.015 mmol, 1.5 mol%) and NaOt-Bu (135 mg, 1.40 mmol). The test tube was fitted with a septum and toluene (2.0 mL), N-methylaniline (135 μL, 1.25 mmol) and 2-chloro-p-xylene (135 μL, 1.01 mmol) were added. The mixture was stirred at 80 °C for 13 hours, then cooled to room temperature, diluted with diethyl ether (20 mL), filtered and concentrated. The crude was purified by flash chromatography on silica gel to afford 202 mg (95%) of a colorless oil.

Embodiment 3

[0817] Synthesis of Di-n-Butyl-p-Toluidine

[0818]

[0819] The oven-dried resealable Schlenk tubes were purged with argon and loaded with Pd 2 (dba) 3 (2.3mg, 0.0025mmol, 0.05mol% Pd), Ligand 2 [Example 1] (2.9mg, 0.0075mmol, 0.075mol%) and NaOt-Bu (1.34g, 13.9mmol). Toluene (10 mL), di-n-butylamine (2.00 mL, 11.9 mmol) and 4-chlorotoluene (1.18 mL, 10.0 mmol) were added and the mixture was degassed with three freeze-pump-thaw cycles. The reaction vessel was placed under an argon atmosphere, sealed with a Teflon screw cap, and stirred at 100°C for 20 hours, after which time GC analysis showed complete consumption of the aryl halide. The reaction mixture was cooled to room temperature, diluted with ether (100 mL) and extracted with 1M HCl (3 x 100 mL). The combined aqueous acid phases were basified with 3M NaOH, then extracted with diethyl ether (3 x 150 mL). The ether extracts were dried over anhydrous sodium sulfate, filtered and concentrated to give 2.01 g (95%) of ...

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Abstract

One aspect of the invention relates to ligands of transition metals. A second aspect of the invention relates to the use of catalysts comprising these ligands in transition metal catalyzed carbon-heteroatom and carbon-carbon bond forming reactions. The method offers many features to transition metal-catalyzed reactions, including suitable substrate scope, reaction conditions and improvements in efficiency.

Description

[0001] Government funding [0002] The US Government has certain rights in this invention, which was made with support under Grant No. 9421982-CHE granted by the National Science Foundation. Background of the invention [0003] Transition metal catalyst complexes play an important role in many fields of chemistry including the preparation of polymers and pharmaceuticals. It is recognized that the properties of these catalyst complexes are influenced both by the properties of the metal and by the properties of the ligands bound to the metal atoms. For example, the structural properties of the ligand can affect reaction rate, regioselectivity, and stereoselectivity. Larger ligands can be expected to slow down the reaction; electron-withdrawing ligands can be expected to slow down oxidative addition to the metal center and accelerate reductive elimination from the metal center in a coupling reaction; conversely, one can expect In a coupling reaction, the electron-rich ligand wi...

Claims

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Application Information

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IPC IPC(8): C07C6/00C07C45/00C07C21/00C07F9/02C07F9/50
Inventor S·L·布赫瓦尔德X·黄D·齐姆
Owner MASSACHUSETTS INST OF TECH
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