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Method for performing gold-catalyzed selective C-H bond functionalization on phenol and aniline

A functionalized and selective technology, applied in the field of C-H bond functionalization with high chemical and regioselectivity, can solve problems such as poor chemical selectivity, achieve less catalyst dosage, maintain yield and catalytic efficiency, and reduce substrates. Wide range of effects

Active Publication Date: 2014-07-23
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

There is an existing literature that mentions the intercalation of carbene to carbon and hydrogen by the decomposition of intramolecular diazo compounds, but its chemoselectivity is not good, and a mixture of oxygen, hydrogen and carbon and hydrogen is obtained.

Method used

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  • Method for performing gold-catalyzed selective C-H bond functionalization on phenol and aniline
  • Method for performing gold-catalyzed selective C-H bond functionalization on phenol and aniline
  • Method for performing gold-catalyzed selective C-H bond functionalization on phenol and aniline

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] Example 1 Synthesis of 2-(4-hydroxyphenyl)-2-phenylacetic acid methyl ester (Methyl2-(4-hydroxyphenyl)-2-phenylacetate)

[0053]

[0054] Step 1: To a pre-dried reaction tube, add (2,4- t Bu 2 C 6 h 3 O) PAuCl (0.02mmol) and previously with CaH 2 Dried CH 2 Cl 2 (4mL), then add AgSbF 6 (0.02 mmol), stirred for 15 minutes. In the second step, phenol (0.6mmol) was first added to the reaction tube, and then the diazo compound (0.4mmol) was pre-dissolved in CaH 2 Dried CH 2 Cl 2 (1mL) then dropwise add the dichloromethane solution of the diazo compound, the whole dropping process continues for 30 minutes, the slower the dropping process, the better, especially at the end of the fast dropwise addition, so as to avoid the spontaneous generation of the diazo compound get together. The entire reaction process should be avoided under strong light conditions to avoid decomposition of the silver salt. After the dropwise addition was completed, stirring was continued...

Embodiment 2

[0055] Example 2 Synthesis of ethyl 2-(4-hydroxyphenyl)-2-phenylacetate (Ethyl2-(4-hydroxyphenyl)-2-phenylacetate).

[0056]

[0057] Operation reference example 1 yield is 99%. 1 H NMR (400MHz, CDCl 3 )δ7.20-7.35(m, 5H), 7.13(d, J=8.4Hz, 2H), 6.71(d, J=8.4Hz, 2H), 5.61(s, 1H), 4.95(s, 1H), 4.20(q, J=7.2Hz, 2H), 1.24(t, J=7.2Hz, 3H); 13 C NMR (100MHz, CDCl 3 )δ173.30154.88, 138.86, 130.58, 129.78, 128.55, 128.41, 127.15, 115.44, 61.36, 56.27, 14.06; MS (EI): m / z (%): 256 (M + , 10.47); 183(100); HRMScalcd.for C 16 h 16 o 3 : HRMS (ESI) calcd.for C 16 h 16 NaO 3 [M+Na]: 279.0992, found: 279.0981.

Embodiment 3

[0058] Example 3 Synthesis of 2-(4-hydroxyphenyl)-2-(4-chlorophenyl)methyl acetate (Methyl2-(4-chlorophenyl)-2-(4-hydroxyphenyl)acetate).

[0059]

[0060] Operation reference example 1 yield is 99%. 1 H NMR (400MHz, CDCl 3 )δ7.28(d, J=8.0Hz, 2H), 7.22(d, J=8.0Hz, 2H), 7.13(d, J=8.0Hz, 2H), 6.76(d, J=8.0Hz, 2H) , 5.13(s, 1H), 4.94(s, 1H), 3.74(s, 3H); 13 C NMR (100MHz, CDCl 3 )δ173.10, 154.97, 137.30, 133.18, 130.26, 129.84, 129.73, 128.71, 115.57, 55.46, 52.49; MS (EI): m / z (%): 276 (M + , 29.32), 278([M+2] + , 9.13); 217(100); HRMS(ESI) calcd.for C 15 h 13 ClNaO 3 [M+Na]: 299.0445, found: 299.0449.

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Abstract

The invention provides a method for performing gold-catalyzed selective C-H bond functionalization on phenol and aniline, which comprises the following steps: by taking phenol and aniline compounds as raw materials and taking phosphine ligand or carbene as ligand, in organic solvent, reacting with a diazo compound in the presence of a gold catalyst and a silver salt, performing carbon-hydrogen bond insertion at the para-position or ortho-position of the phenol or aniline structure. The method provided by the invention has the characteristics of low catalyst consumption, mild conditions, wide substrate application range and the like; the method can be used for quickly and efficiently synthesizing methyl acetate derivatives containing the phenol or aniline structure; and meanwhile, the method can be used for performing later modification on natural products or drug molecules (such as estrone), or be used for synthesizing some molecules having biological activity, thus having favorable application prospects.

Description

technical field [0001] The invention relates to the technical field of chemical industry, in particular to a gold-catalyzed high chemical and regioselective C-H bond functionalization method for phenol and aniline. Background technique [0002] Phenol or aniline structural units, and α-bisaryl substituted esters containing phenol aniline structural units and their derivatives are widely found in many natural products and drug molecules, as shown below, and this type of structure is also a very important class of organic synthesis Building blocks are widely used in synthetic organic chemistry. [0003] [0004] Therefore, starting from cheap and easy-to-obtain raw materials such as phenol and aniline, the development of new direct C-H bond functionalization with a wide range of applications and high chemoselectivity and regioselectivity is of great significance for organic synthetic chemistry. At the same time, it also provides a possibility for structural modification of...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/00C07C67/343C07C69/732C07C69/734C07D333/24C07D209/34C07C231/12C07C235/38C07C45/68C07C49/83C07C253/30C07C255/36C07C201/12C07C205/17C07C233/54C07C235/80C07C233/81C07C269/06C07C271/28C07C235/34C07J1/00
Inventor 张俊良刘路余谆谆马奔陈明金
Owner EAST CHINA NORMAL UNIV
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