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A kind of method for synthesizing tri-substituted alkenyl borate by copper-catalyzed three-component reaction

A technology of alkenyl borate and tri-substitution, which is applied in the field of synthesizing alkenyl borate, can solve the problems that the synthesis of tri-substituted alkenyl borate has not yet been realized, and achieve wide application range of substrates, high yield, Simple Effects of React Raw Materials

Active Publication Date: 2022-07-05
CHANGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] Borylation of N-sulfonylhydrazones with boron reagents is also an effective method for the synthesis of organoboron compounds (Li, H.; Wang, L.; Zhang, Y.; Wang, J. Angew. Chem., Int. Ed. 2012 ,51,2943.Li,H.; Shangguan,X.; Zhang,Z.; Huang,S.; Zhang,Y.; Wang,J.Org.Lett.2014,16,448.), although the synthesis of alkenyl boronic acid There are many methods for esters, but the synthesis of trisubstituted alkenyl boronic acid esters by three-component one-pot reaction with difunctionalization at the same alkyne terminal carbon has not yet been realized.

Method used

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  • A kind of method for synthesizing tri-substituted alkenyl borate by copper-catalyzed three-component reaction
  • A kind of method for synthesizing tri-substituted alkenyl borate by copper-catalyzed three-component reaction
  • A kind of method for synthesizing tri-substituted alkenyl borate by copper-catalyzed three-component reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Example 1: Synthesis of 4a:

[0032]

[0033] Under the protection of argon, add 1a (20.4 mg), B to the reaction tube 2 (pin) 2 (152.3 mg), CuI (3.1 mg), 2,2'-bipyridine (3.1 mg), Molecular sieves (100 mg) and DMF (2 mL) were added followed by 2a (52.8 mg) dissolved in DMF (2 mL); the reaction mixture was stirred on a 30°C heating block for 18 hours. The reaction solution was diluted with 10 mL of water and extracted with ethyl acetate; the organic phase was dried and the solvent was removed under reduced pressure; the crude product was purified by column chromatography, eluted with ethyl acetate: petroleum ether (1:20) to obtain a colorless oily product 4a (66.6 mg, 88%, Z:E>19:1). 1 H NMR(300MHz, CDCl3)δ7.49(s,1H),7.33-7.26(m,6H),7.26-7.17(m,4H),4.89(s,1H),3.67(s,3H),1.30( s,6H), 1.29(s,6H). 13C NMR (75MHz, CDCl3)δ173.8,144.4,139.5,137.1,129.4,128.8,128.34,128.3,127.7,126.9,83.9,52.2,51.2,24.9,24.8.HRMS(ESI)m / z:[M+Na] +Calcd for C 23 H 27 BNaO 4 401.1895...

Embodiment 2

[0034] Example 2: Synthesis of 4a:

[0035]

[0036] Under the protection of argon, add 1a (20.4 mg), B to the reaction tube 2 (pin) 2 (152.3 mg), CuI (3.1 mg), 2,2'-bipyridine (3.1 mg), Molecular sieves (100 mg) and DMSO (2 mL) were added followed by 2a (52.8 mg) dissolved in DMSO (2 mL); the reaction mixture was stirred on a 30°C heating block for 18 hours. The reaction solution was diluted with 10 mL of water and extracted with ethyl acetate; the organic phase was dried and the solvent was removed under reduced pressure; the crude product was purified by column chromatography, eluted with ethyl acetate: petroleum ether (1:20) to obtain a colorless oily product 4a (30.2 mg, 40%, Z:E>19:1).

Embodiment 3

[0037] Example 3: Synthesis of 4a:

[0038]

[0039] Under the protection of argon, add 1a (20.4 mg), B to the reaction tube 2 (pin) 2 (101.5 mg), CuI (3.1 mg), 2,2'-bipyridine (3.1 mg), Molecular sieves (100 mg) and DMF (2 mL) were added followed by 2a (52.8 mg) dissolved in DMF (2 mL); the reaction mixture was stirred on a 30°C heating block for 18 hours. The reaction solution was diluted with 10 mL of water and extracted with ethyl acetate; the organic phase was dried and the solvent was removed under reduced pressure; the crude product was purified by column chromatography, eluted with ethyl acetate: petroleum ether (1:20) to obtain a colorless oily product 4a (38.6 mg, 51%, Z:E>19:1).

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Abstract

The invention belongs to the field of organic synthesis, and in particular relates to a method for synthesizing tri-substituted alkenyl boronate by copper-catalyzed three-component reaction, and provides a stereoselective copper-catalyzed terminal alkyne, double pinacol boronate and heavyweight A method for one-pot synthesis of trisubstituted alkenyl boronate esters from nitrogen compounds or N-sulfonyl hydrazones. This method selectively difunctionalizes the terminal end of the terminal alkyne. When using a diazo compound as a carbene precursor, a (Z)-trisubstituted alkenyl boronate is obtained with high stereoselectivity, and when an N-sulfonyl hydrazone is used, it is obtained (E)-Tri-substituted alkenyl borate. The method of the invention has the following advantages: a three-component series-connected one-pot reaction, simple operation, simple and easy-to-obtain raw materials, high reaction yield, wide substrate application range, and good and controllable (E) / (Z) stereoselectivity.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for synthesizing alkenyl boronate by one-pot method using copper-catalyzed terminal alkyne, bispinacol boronate and diazo compound or sulfonylhydrazone. Background technique [0002] Organoboronates are a class of organic reagents with important synthetic application value and are widely used in cross-coupling reactions. As the most common synthons of complex alkene derivatives, alkenyl boronate esters can be used to synthesize target molecules containing alkenyl groups. At present, the main method for synthesizing alkenyl boronic esters is prepared by metal-catalyzed boronation of alkenes, allenes or alkynes with boron reagents (Moure, A.L., et al.J.Am.Chem.Soc.2012,134,7219 .Reid, W.B.;, et al.Org.Lett.2018,20,6832.Magre,M.,et al.Angew.Chem.Int.Ed.2019,58,7025.Brzozowska,A.,et al.Org. Lett.2020,22,3765.Guo,W.-H.,et al.ACSCatal.2019,9,38.Hu,Y.,et al.Angew....

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F5/02
CPCC07F5/025C07B2200/09
Inventor 孙江涛许光洋李自永邵莺唐生表
Owner CHANGZHOU UNIV
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