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Nitrogen heterocycle ligand transition metal complex, and preparation and catalytic application thereof

A transition metal and nitrogen heterocyclic technology, applied in the field of nitrogen-containing heterocyclic ligands, can solve the problems of low selectivity and ineffective catalysis of catalysts, and achieve the effect of simple synthesis method

Active Publication Date: 2012-04-18
ENANTIOTECH CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, hindered ketones and esters show different structural characteristics from other ketones and esters, and many catalysts cannot catalyze effectively and their selectivity is not high
Therefore, the efficient and highly selective asymmetric catalytic hydrogenation of hindered ketones or esters is currently a great challenge.

Method used

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  • Nitrogen heterocycle ligand transition metal complex, and preparation and catalytic application thereof
  • Nitrogen heterocycle ligand transition metal complex, and preparation and catalytic application thereof
  • Nitrogen heterocycle ligand transition metal complex, and preparation and catalytic application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Embodiment 1: the preparation of isoquinoline ammonia ligand

[0047]

[0048] Preparation of 2-aminomethylisoquinoline (7)

[0049] Add 2-cyanoisoquinoline (0.8 g) and 80 ml of methanol into the hydrogenation kettle, and stir to suspend 10% Pd / C (0.8 g). Displacing air, passing H 2 , pressurized to 5 atmospheres, and stirred for 16 hours. After the reaction was completed, filter with diatomaceous earth, and wash the filter cake with methanol. The resulting mother liquor was concentrated to dryness, then dissolved with 9 ml of absolute ethanol, saturated with hydrogen chloride gas, then cooled to 5°C, and a solid was precipitated, filtered, and dried to obtain 2-aminomethylisoquinoline (7) hydrochloride Salt 449 mg.

[0050] Preparation of 1-aminomethylisoquinoline (8)

[0051] 1-Aminomethylisoquinoline (8) can be prepared by the same process.

[0052]

Embodiment 2

[0053] The preparation of embodiment 2 isoquinoline ammonia ligand 14

[0054]

[0055]

[0056] Preparation of 2-acetylisoquinoline (11)

[0057] Intermediate 9 (800 mg) was placed in a 100 ml three-necked flask, and after replacing the air, 20 ml of dried THF was added, cooled to -78°C, and MeMgBr was slowly added. After the addition was completed, the temperature was slowly raised to -40°C, and the reaction was carried out for 100 minutes. After TLC monitors that the reaction is complete, the saturated ammonium chloride aqueous solution quenches the reaction, extracts with 250 milliliters of ethyl acetate, sherwood oil / ethyl acetate (10 / 1) passes through the column, and separates to obtain 2-acetyl isoquinoline (11), 502 mg white solid, yield 80%.

[0058] Preparation of (S)-1-(isoquinoline)ethanol (12)

[0059] Intermediate 11 (170 mg), RuCl2[(R)-xyl-Binap][(R)-Daipen] (1 mg), t-BuOK (6 mg) were added to the reaction kettle, after degassing, 3 ml of iso propanol....

Embodiment 3

[0064] Synthesis of the procatalyst of embodiment 3: RuCl 2 [(S)-BINAP]DMF 2

[0065]

[0066] [RuCl 2 (η 6 -benzene)] 2 (6.5 mg), 1 equivalent of (S)-BINAP (16.3 mg) dissolved in 2.0 mL of DMF, transferred to a 10 mL Schlenk tube under argon atmosphere and degassed. After the suspension was heated at 100°C for 30 minutes, it was cooled to room temperature, and the solvent was removed to obtain a solid product, which was dried under vacuum at 50°C for 2 hours.

[0067] RuCl 2 [(S)-binap] dmf 2 、RuCl 2 [(S)-Tolbinap] dmf 2 、RuCl 2 [(R)-xylbinap]dmf 2 、RuCl 2 [(S,S)-Skewphos]dmf 2 、RuCl 2 [(S)-phanephos]dmf 2 、RuCl 2 [(S,S)-Dipamp]dmf 2 、RuCl 2 [(S,S)-Chiraphos]dmf 2 、RuCl 2 [Mondyphos] dmf 2 、RuCl 2 [(S)-Segphos]dmf 2 、RuCl 2 [(S,S)-Diop]dmf 2 etc. can be prepared in a similar manner.

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Abstract

The invention relates to a novel nitrogen heterocycle ligand / phosphine ligand transition metal complex, and preparation and application thereof in asymmetric catalytic hydrogenation and hydrogen transfer. The complex has the following structural formula: [MLnL' XY], wherein the transition metal M is Ru, Rh, Ir, Pd, Pt, Co, Ni or Os. The complex also contains a nitrogen heterocycle ligand, two monophosphine ligands or one diphosphine ligand, and the like. The transition metal compound, dinitrogen or mononitrogen ligand and diphosphine or monophosphine ligand react at 0-120 DEG C in an organic solvent for 0.5-20 hours to obtain the complex. The complex is used for asymmetric catalytic transfer hydrogenation or asymmetric hydrogenation reaction, and especially for asymmetric catalytic hydrogenation reaction of ketones, esters, hypnones and derivatives thereof, diphenyl ketones and derivatives thereof, beta-N,N-dimethylamino-alpha hypnones and derivatives thereof and other ketone compounds of which the alpha site is a large steric hindrance alkyl group.

Description

technical field [0001] The invention relates to the preparation of a novel nitrogen-containing heterocyclic ligand and phosphine ligand transition metal complex and its application in asymmetric catalytic hydrogenation and hydrogen transfer. Background technique [0002] The conversion of latent chiral ketones or esters to chiral alcohols is a very important class of chemical reactions, which have a very wide range of applications in industry and academia. Transition metal-catalyzed asymmetric reactions are an important tool for the synthesis of optically pure compounds, and have obvious advantages over other processes, such as high efficiency, high selectivity, low pollution, and high atom economy. [0003] Since a series of epoch-making great achievements discovered by Knowles, Sabacky, Kagan, Dang, Noyori, Horner and other scholars, hundreds of catalytic systems have been successfully developed. Notably, no one catalyst is universal, mainly because the reaction substrate...

Claims

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Application Information

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IPC IPC(8): C07F19/00C07F15/00C07F15/06C07F15/04B01J31/24C07B41/02C07C29/145C07C31/125C07C33/22C07C33/24
CPCC07B2200/07B01J2231/643C07C2102/08C07C2101/14B01J31/2452C07B41/02C07C29/145B01J2531/821C07F15/0053B01J31/183C07C2601/14C07C2602/08
Inventor 刘毓宏徐亮
Owner ENANTIOTECH CORP
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