3-(substituted bisulfonyl fluromethane)-1-propylene compound, synthetic method and applications thereof

A technology of disulfonyl fluoromethane and compound, which is applied in the field of allyl alkylation reaction, can solve problems such as unsolvable regioselectivity, and achieve the effects of unique physiological activity, mild reaction conditions and simple operation.

Inactive Publication Date: 2009-10-28
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The palladium catalytic system not only cannot solve the difficult problem of regioselectivity, but also when the product is derivatized and reduced to remove the sulfonyl group, the double bond will often be reduced due to the existence of the conjugated double bond.

Method used

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  • 3-(substituted bisulfonyl fluromethane)-1-propylene compound, synthetic method and applications thereof
  • 3-(substituted bisulfonyl fluromethane)-1-propylene compound, synthetic method and applications thereof
  • 3-(substituted bisulfonyl fluromethane)-1-propylene compound, synthetic method and applications thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Example 1: Research on the temperature and solvent of Friedel-Crafts allyl alkylation of diphenylsulfonyl fluoride with methane compounds under the catalysis of iridium complexes:

[0030]

[0031] Among them, mol refers to mole, base refers to alkali, solvent refers to solvent, and rt refers to room temperature.

[0032]

[0033]

[0034] Among them, THF is tetrahydrofuran, toluene is toluene, dioxane is dioxane, DCE is dichlorohexane, DCM is dichloromethane, Et 2 O is ether, MeCN is acetonitrile, CDCl 3 It is deuterated chloroform, DBU is 1,8-diazabicyclo[5,4,0]undec-7-ene, DABCO is triethylenediamine, urotropine is urotropine; used for serial number 1-10 The amount of alkali is 1.1 times of consumption, and sequence number 11-17 is 2.2 times of consumption.

Embodiment 2

[0035] Example 2: Research on the allylic alkylation of diphenylsulfonyl fluoromethane with different ligands under the catalysis of iridium complex:

[0036]

[0037] 1a R 3 , R 4 = Ph 1d R 3 , R 4 =Ph 1e R 5 = i Pr, Ar=Ph

[0038] 1b 3 , R 4 = 2-Naphthyl

[0039] 1c 3 , R 4 =2-MeO-Ph

[0040]

[0041] Where Ph is phenyl, Naphthyl is naphthyl, MeO is methoxy, i Pr is isopropyl.

Embodiment 3

[0042] Example 3: Diphenylsulfonyl fluoromethane compounds and allyl carbonate undergo allyl alkylation under the catalysis of metal iridium complexes

[0043]

[0044] Add [Ir(COD)Cl] sequentially to a dry reaction tube 2 (0.004mmol), chiral ligand (0.008mmol), n-propylamine (0.5mL) and THF (0.5mL), reacted at 50°C for 20 minutes, then naturally cooled to room temperature and pumped dry. Diphenylsulfonylfluoromethane (0.2mmol), cesium carbonate (0.5mmol), allyl carbonate (0.22mmol), and DCM (2mL) were added to the reaction tube in turn, and the reaction was stirred at room temperature. After the reaction, the solvent was removed under reduced pressure and the residue was separated by column chromatography to obtain the product (ethyl acetate / petroleum ether=1 / 5-1 / 2, v / v).

[0045] P1: 3-(diphenylsulfonylfluoromethyl)-phenylprop-1-ene

[0046]

[0047] White solid, melting point: 127-129°C; 89% yield, 94% ee; [chiral column OD-H (0.46cmx 25cm); n-hexane / isopropanol=98 / ...

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Abstract

The invention provides a 3-(substituted bisulfonyl fluromethane)-1-propylene compound, a synthetic method and applications thereof. The method is an effective method for synthesizing the optically active 3-(substituted bisulfonyl fluromethane)-1-propylene compound with iridium complex as catalyst and allyl carbonic ester and diphenylsulfonyl fluomethane compound in a highly regional and highly enantioselective manner. The catalyst is easy to obtain and has high activity; the reaction conditions are mild; a substrate has a wide application range and the products have high regional and enantioselectivity. The synthesized 3-(substituted bisulfonyl fluromethane)-1-propylene compound is easy for preparing fluorochemicals which contain aldehyde, alcohol, amine, carboxylic acid or poly-cycle, arewidely applied to pesticides and drugs and have special physiological activities in a chemical way.

Description

technical field [0001] The invention relates to an allyl alkylation reaction of disulfonyl fluoromethane compounds and allyl carbonate catalyzed by metal complexes, which can be synthesized with high efficiency, high regio and enantioselectivity 3-Disulfonylfluoromethane substituted-1-propene compounds. The present invention relates to the synthesis of aldehydes, aldehydes, alcohols and amines containing monofluoromethyl groups by substituted 1-propene compounds with 3-disulfonyl fluoromethane through sulfonyl group removal, oxidation, diammonization, cyclization and other chemical pathways , carboxylic acid or polycyclic drug intermediates with special physiological effects. Background technique [0002] In drug design, the monofluoromethyl block is of great significance for the design of isoelectronic arrangement drugs, and the compound containing a monofluoromethyl unit plays an important role [a) Organofluorine Chemistry: Principles and Commercial Applications (Eds. : ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C317/10C07C317/18C07D333/18C07C317/08C07C317/24C07D209/34C07D333/22C07D337/14C07D263/57C07D207/20C07D209/88C07B53/00C07C315/04B01J31/24C07C22/08C07C17/35C07C43/225C07C41/18C07C57/58C07C59/64C07C51/265
Inventor 游书力刘文博
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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