Preparation method of olefin and method for synthesizing Chondriamide A and Chondriamide C

An olefin and hydrocarbon-based technology, applied in the preparation of organic compounds, the preparation of amino compounds from amines, the preparation of carbon-based compounds, etc., can solve the problems of high reaction temperature and environmental pollution, and achieve the advantages of simple operation, cost reduction, and simplified treatment methods. Effect

Active Publication Date: 2018-08-24
UNIV OF SCI & TECH OF CHINA
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] At present, reports on the reaction of aliphatic carboxylic acid decarboxylation to olefins are quite extensive, such as palladium catalysis (Angew.Chem.Int.Ed.2015, 54, 11800-11803), copper catalysis (Angew.Chem.Int.Ed.2017, 56, 7648-7652), etc., but some of the currently disclosed reactions to prepare olefins from aliphatic carboxylic acid decarboxylation require higher reaction temperatures (130° C.), or use equivalent heavy metal catalysts (equivalent lead acetate), which are harmful to the environment. It caused relatively large pollution; therefore, it is of great significance to prepare corresponding olefins through low-pollution means using carboxylic acids widely existing in nature, which is in line with the requirements of green chemistry.

Method used

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  • Preparation method of olefin and method for synthesizing Chondriamide A and Chondriamide C
  • Preparation method of olefin and method for synthesizing Chondriamide A and Chondriamide C
  • Preparation method of olefin and method for synthesizing Chondriamide A and Chondriamide C

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preparation example Construction

[0043] The invention provides a kind of preparation method of olefin, comprising:

[0044] Mixing a compound of formula (I), a palladium catalyst, a phosphorus ligand, a base, and an organic solvent for light reaction at room temperature to obtain an alkene having a structure of formula (II);

[0045]

[0046] Among them, R 1 C1-C50 alkyl group, C1-C50 heteroatom-containing alkyl group, C2-C50 unsaturated hydrocarbon group, C2-C50 heteroatom-containing unsaturated hydrocarbon group or C3-C50 aromatic group;

[0047] X is a hydrogen atom, methylene, oxygen or nitrogen;

[0048] When X is a hydrogen atom, R 2 group does not exist;

[0049] When X is methylene, oxygen or nitrogen, R 2 C1-C50 alkyl group, C1-C50 heteroatom-containing alkyl group, C2-C50 unsaturated hydrocarbon group, C2-C50 heteroatom-containing unsaturated hydrocarbon group, C3-C50 aromatic group or X and R 2 Form a five- or six-membered ring;

[0050] or R 1 , X and their carbons form a ring;

[0051...

Embodiment 1

[0078] Embodiment 1, preparation 1-pentadecene

[0079] Reaction formula:

[0080]

[0081] The specific method is as follows:

[0082] Add photocatalyst palladium chloride (2mol%, 0.7mg), 4,5-bis-diphenyl Phosphine-9,9-dimethylxanthene (L1) (3mol%, 3.5mg), 2-(dicyclohexylphosphino)biphenyl (L2) (4mol%, 2.8mg) and active aliphatic NHPI Ester (0.2 mmol, 80.2 mg). The air in the tube was completely replaced with argon three times, and then 2,4,6-collidine (0.2 mmol, 24.2 mg), 2 mL of N,N-dimethylacetamide (DMA) were added under argon atmosphere. The reaction system was continuously stirred at room temperature for 15 hours under the irradiation of a 36W blue LED lamp (IKA magnetic stirrer, RCT basic type, stirring speed 500 rpm). After the reaction is complete, use H 2The reaction was quenched with O, and the reaction solution was extracted with ethyl acetate (3*10 mL), and then the combined organic phase was concentrated by rotary evaporation (BUCHI Co., Ltd., BUCHI rota...

Embodiment 2

[0086] Embodiment 2, preparation Z-octadeca-1,8-diene

[0087] Reaction formula:

[0088]

[0089] Method is with example 1, and productive rate sees figure 1 .

[0090] Utilize nuclear magnetic resonance to analyze the Z-octadeca-1,8-diene obtained in embodiment 2, obtain the result:

[0091] 1 H NMR (400MHz, CD2Cl2) δ5.81 (ddt, J=16.9, 10.2, 6.7Hz, 1H), 5.38-5.33(m, 2H), 5.04-4.90(m, 2H), 2.08-1.98(m, 6H ), 1.41-1.25(m, 18H), 0.88(t, J=6.9Hz, 3H).

[0092] 13 C NMR (101MHz, CD2C12) δ139.2, 130.0, 129.8, 114.2, 33.8, 31.9, 29.8, 29.6, 29.5, 29.3, 28.9, 28.8, 27.2, 27.1, 22.7, 14.1.(one carbon signal is overlapped)

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Abstract

The invention provides a preparation method of olefin and a method for synthesizing Chondriamide A and Chondriamide C. The preparation method of olefin comprises the steps as follows: a compound withthe structure shown in a formula (I), a palladium catalyst, a phosphorus ligand, alkali and an organic solvent are mixed and react at the normal temperature under light, and olefin with the structureshown in a formula (II) is obtained. Through selection of the specific phosphorus ligand, the method can realize efficient catalytic conversion at the room temperature under the action of photocatalysis, has mild reaction conditions, is simple to operate, meets the requirement for developing green and environment-friendly chemistry, and has more universal substrate selection range and functional group compatibility and excellent chemical selectivity. The method can be successfully applied to a scheme for introducing C-C double bonds in complex molecules and a synthesis strategy for optimizingpart of drug molecules, can improve the synthesis efficiency and reduce the cost and has industrial synthesis value and prospects.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for preparing olefins and synthesizing Chondriamide A and Chondriamide C by decarboxylation of aliphatic carboxylic acids. Background technique [0002] Alkenes are a very important class of synthetic intermediates in organic chemistry. Various other groups can be easily introduced through the reaction of alkenes, such as the preparation of halogenated compounds through addition reactions, and the preparation of cyclic compounds through D-A reactions; on the other hand, alkenes are also Various coupling reactions can occur through Heck reaction, Suzuki reaction, etc. It is widely used in the field of synthesis. [0003] At present, reports on the reaction of aliphatic carboxylic acid decarboxylation to olefins are quite extensive, such as palladium catalysis (Angew.Chem.Int.Ed.2015, 54, 11800-11803), copper catalysis (Angew.Chem.Int.Ed.2017, 56, 7648-7652), etc., but s...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C1/32C07C11/02C07C11/12C07C13/48C07C15/02C07C41/18C07C43/215C07C43/205C07C43/225C07C209/68C07C211/52C07D211/70C07D307/88C07D307/79C07D265/30C07D207/20C07F5/02C07J9/00C07C45/67C07C49/796C07C269/06C07C271/22C07C271/20C07C271/10C07D209/18C07D209/48C07D209/14B01J31/24
CPCB01J31/24B01J31/2409B01J31/2447C07C1/323C07C41/18C07C45/67C07C209/68C07C269/06C07D207/20C07D209/14C07D209/18C07D209/48C07D211/70C07D265/30C07D307/79C07D307/88C07F5/025C07J9/00C07C2602/10C07C11/02C07C11/12C07C13/48C07C15/02C07C43/215C07C43/205C07C43/225C07C211/52C07C49/796C07C271/22C07C271/20C07C271/10
Inventor 傅尧贺超尚睿成万民王光祖
Owner UNIV OF SCI & TECH OF CHINA
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