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Bidentate aza-carbene manganese catalyst and preparation method and alkylation synthesis application thereof

A carbene manganese catalyst, bidentate azacard technology, which is used in the preparation of amino compounds by condensation/addition reactions, catalytic reactions, carbon-based compounds, etc., can solve the problems of unfriendly environment, less manganese complexes, etc. Simple steps, stable air, high efficiency

Active Publication Date: 2018-12-21
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are relatively few manganese complexes that can be applied to the alkylation reaction of the "hydrogen borrowing reaction" strategy, and in the existing literature reports, the manganese catalysts used in this type of reaction all contain phosphorus in the structure, which is very unfriendly to the environment.

Method used

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  • Bidentate aza-carbene manganese catalyst and preparation method and alkylation synthesis application thereof
  • Bidentate aza-carbene manganese catalyst and preparation method and alkylation synthesis application thereof
  • Bidentate aza-carbene manganese catalyst and preparation method and alkylation synthesis application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] Example 1: Synthesis of bidentate azaimidazole iodine salt ligand 2a

[0049]Into a sealed 15mL tube, weigh 1.97g (1.91mL, 24mmol) of 1-methylimidazole, 3.21g (0.96mL, 12mmol) of diiodomethane, and 5mL of tetrahydrofuran, and react at 110°C for 24h. During the reaction, white Solid is separated out gradually; After reaction finishes, be cooled to room temperature, filter, solid is washed with tetrahydrofuran, then rinses with a large amount of methylene chloride, finally dry to obtain 5g white solid product, i.e. bidentate azaimidazole iodonium ligand 2a, yield is 96%.

[0050] 1 H NMR (400MHz, DMSO-d 6 ) δ 9.40 (s, 2H), 7.99 (t, J = 1.7Hz, 2H), 7.81 (t, J = 1.6Hz, 2H), 6.67 (s, 2H), 3.90 (s, 6H).

[0051] 13 C NMR (101MHz, DMSO-d 6 ) δ 137.96, 124.31, 121.83, 121.74, 58.06, 36.37.

Embodiment 2

[0052] Example 2: Synthesis of azaimidazole iodine salt ligand 2b

[0053] According to the synthesis method of ligand 2a in Example 1, 4.47g (24mmol) 1-s-trimethylphenylimidazole was used instead of 1-methylimidazole, and other operating conditions were the same as in Example 1. After the reaction, 6.9g of white solid product was obtained. , that is, the bidentate azaimidazole iodide ligand 2b, with a yield of 90%.

[0054] 1 H NMR (400MHz, DMSO-d 6 )δ9.82(s, 2H), 8.38(t, J=1.6Hz, 2H), 8.11(t, J=1.6Hz, 2H), 7.18(s, 4H), 6.89(s, 2H), 2.34( s,6H), 2.05(s,12H).

[0055] 13 C NMR (101MHz, DMSO-d 6 ) δ 140.56, 139.01, 134.16, 130.78, 129.31, 124.83, 122.79, 59.27, 20.59, 17.00.

Embodiment 3

[0056] Example 3: Synthesis of bidentate azaimidazole iodine salt ligand 2c

[0057] According to the synthesis method of ligand 2a in Example 1, 3.46g (24mmol) 1-phenylimidazole was used to replace 1-methylimidazole, and other operating conditions were the same as in Example 1. After the reaction, 6.13g of a light brown solid was obtained, i.e. bis Dental azaimidazole iodonium ligand 2c, the yield is 92%.

[0058] 1 H NMR (400MHz, DMSO-d 6 )δ10.11(s, 2H), 8.45(s, 2H), 8.30(s, 2H), 7.82(d, J=7.9Hz, 4H), 7.72(t, J=7.7Hz, 4H), 7.65( t, J=7.3Hz, 2H), 6.85(s, 2H).

[0059] 13 C NMR (101MHz, DMSO-d 6 ) δ 137.25, 134.41, 130.31, 130.27, 123.02, 122.04, 121.81, 58.82.

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Abstract

The invention discloses a bidentate aza-carbene manganese catalyst and a preparation method and alkylation synthesis application thereof. The catalyst disclosed by the invention has a wide accommodation range to a substrate and can be used for catalyzing the synthesis of C-C and C-N bond compounds of different structures under a moderate condition, alcohol is directly taken as a raw material for reaction, and a reactant can be easily obtained and is reproducible. Compared with a traditional aldehyde reactant, the catalyst disclosed by the invention is more stable, easy to operate, low in toxinand environmentally-friendly.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a bidentate azacarbene manganese catalyst, a preparation method thereof and an alkylation synthesis application. Background technique [0002] Alkylation reaction is a very important reaction for constructing C-X bond (X=C or N), and has a wide range of applications in the synthesis of natural products, materials and drugs. Traditional alkylation reactions require the use of highly toxic organohalogen reagents and excess alkali, accompanied by a large number of by-products and wastes, which have a greater impact on the environment. In recent years, the "hydrogen borrowing reaction" strategy catalyzed by transition metal catalysts using alcohols as alkylating agents has shown great advantages in alkylation reactions. The strategy is specifically divided into three steps: first, alcohols are dehydrogenated into aldehydes / ketones under the action of metal catalysts; then ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07C209/60C07C211/52C07C211/58C07C213/02C07C217/58C07C217/84C07D213/74C07C211/48C07D319/18C07C211/61C07C45/68C07C49/784C07C49/813C07C49/84
CPCB01J31/2273B01J2231/4205B01J2231/4283B01J2531/0233B01J2531/72C07C45/68C07C209/60C07C213/02C07D213/74C07D319/18C07C2603/18C07C211/48C07C211/52C07C211/58C07C211/61C07C49/784C07C49/813C07C49/84C07C217/58C07C217/84
Inventor 柯卓锋黄明李玉葵兰小兵
Owner SUN YAT SEN UNIV