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Method for deoxygenated functionalization and deoxygenated activation of alcohols and alcohol-functionalized substances

A deoxidation function and activator technology, which is applied in the preparation of amino compounds from amines, organic chemistry, bulk chemical production, etc., can solve the problems that do not conform to the principle of atom economy, the difficulty of separating phosphine oxide by-products, the limitation of the range of nucleophiles, etc. problems, to achieve the effect of wide application range of substrates, easy separation and purification, and simple operation

Pending Publication Date: 2022-07-08
山东博苑医药化学股份有限公司 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Appel reaction and Garegg–Samuelsson reaction (J.Am.Chem.Soc.2007,129,9566-9567; J.Chem.Soc., Perkin Trans.1 1980,2866-2869) are effective methods for hydroxyhalogenation, but Use of highly toxic CX4 reagents or generation of difficult-to-separate phosphine oxide by-products
Mitsunobu reaction (Chem.Rev.2009,109,2551-2651) is a common method for alcohol deoxygenation functionalization, but it has the characteristics of alcohol configuration inversion, and it needs acidic nucleophile, which has some restrictions on the range of nucleophile. limit, and will produce phosphine oxide by-products that are difficult to separate, which does not conform to the principle of atom economy

Method used

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  • Method for deoxygenated functionalization and deoxygenated activation of alcohols and alcohol-functionalized substances
  • Method for deoxygenated functionalization and deoxygenated activation of alcohols and alcohol-functionalized substances
  • Method for deoxygenated functionalization and deoxygenated activation of alcohols and alcohol-functionalized substances

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Experimental program
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Effect test

specific Embodiment approach 1

[0122] The functionalization is amination, the nucleophile is a nitrogen-containing nucleophile, and the method comprises:

[0123] (1) in the first solvent, in the presence of an activator, the alcohol is deoxidized and activated to obtain an iodide intermediate;

[0124] (2) Functionalizing the iodide intermediate in a second solvent in the presence of a nitrogen-containing nucleophile.

[0125] Preferably, the activator is trimethyliodosilane.

[0126] Preferably, the nitrogen-containing nucleophile is selected from the group consisting of azide salts, amides, sulfonamides, primary aliphatic amines, secondary acyclic or cyclic aliphatic amines, primary aromatic amines, secondary aromatic amines and aza aromatic rings at least one of them.

[0127] Preferably, the amination functionalization is represented by the following formula (2):

[0128]

[0129] Among them, in formula (2), R 1 and R 2 with the aforementioned R 1 and R 2 The definitions correspond to the sam...

specific Embodiment approach

[0132] The nitrogen-containing nucleophile is an azide salt; the second solvent is DMF, and the functionalization conditions include: a temperature of 20-60° C. and a time of 2-16 hours.

[0133] According to another preferred embodiment of the present invention:

[0134] The nitrogen-containing nucleophile is selected from at least one of primary aliphatic amines, secondary (acyclic or cyclic) aliphatic amines, primary aromatic amines, secondary aromatic amines and nitrogen heteroaromatic rings; the second The solvent is acetonitrile, and the functionalization conditions include: heating under reflux, the temperature is 20-100°C, and the time is 0.5-20h.

[0135] According to another preferred embodiment of the present invention:

[0136] The iodide intermediate is a chiral iodide, the nitrogen-containing nucleophile is an azide salt, the amination reaction product is a chiral azide product, and the chiral azide product is the same as the chiral azide product. The optical c...

specific Embodiment approach 2

[0137] The functionalization is sulfurization, the nucleophile is a sulfur-containing nucleophile, and the method includes:

[0138] (1) in the first solvent, in the presence of an activator, the alcohol is deoxidized and activated to obtain an iodide intermediate;

[0139] (2) Functionalizing the iodide intermediate in a second solvent in the presence of a sulfur-containing nucleophile.

[0140] Preferably, the activator is trimethyliodosilane.

[0141] Preferably, the sulfur-containing nucleophile is selected from at least one of aliphatic thiol, substituted or unsubstituted thiophenate, substituted or unsubstituted thiophenol, heteroarylthiol and sodium phenylsulfinate , the optional substituent is selected from at least one of halogen, alkyl, alkoxy, aryl, and amine.

[0142] Preferably, the sulfur functionalization reaction is represented by the following formula (3):

[0143]

[0144] Among them, in formula (3), R 1 and R 2 with the aforementioned R 1 and R 2 T...

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Abstract

The invention relates to the field of organic synthesis, and discloses a method for deoxidation functionalization and deoxidation activation of alcohol and an alcohol functionalization material.The method comprises the steps that 1, in a first solvent, in the presence of an activating agent, alcohol is subjected to deoxidation activation, and an iodo intermediate is obtained; and (2) functionalizing the iodo intermediate in a second solvent in the presence of a nucleophilic reagent. The method provided by the invention is simple and convenient to operate and easy to separate and purify.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for deoxyfunctionalizing and deoxyactivating alcohol and an alcohol functionalized substance. Background technique [0002] As a class of inexpensive and readily available compounds, the deoxyfunctionalization of alcohols has always been a research hotspot in the fields of organic synthetic chemistry and medicinal chemistry. According to the formation method of chemical bond breaking during the reaction process, the deoxyfunctionalization of alcohols is mainly divided into polarization reaction process (Tetrahedron Lett. 1985, 26, 757-760; J.Am.Chem.Soc.2020,142,16787-16794) and metal-catalyzed reaction process (J.Am.Chem.Soc.2012,134,14638-14641; Chem.Commun.2015, 51, 2683-2686). [0003] Among them, direct nucleophilic substitution is the most ideal way, H 2 O, as the only by-product, combines the advantages of environmental friendliness and atom economy. However, ...

Claims

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Application Information

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IPC IPC(8): C07C247/10C07C209/68C07C211/27C07D295/03C07C319/14C07C321/28
CPCC07C247/10C07C209/68C07D295/03C07C319/14C07C211/27C07C321/28Y02P20/55
Inventor 汪清民李成林于国清陈育明宋红健何如刘玉秀
Owner 山东博苑医药化学股份有限公司
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