Clicking Azides and Alkynes with Poly(pyrazolyl)borate-Copper(I) Catalysts: An Experimental and Computational Study

被引：6

作者：

Bahsis, Lahoucine ^{[1
]}

Ben El Ayouchia, Hicham ^{[1
]}

Anane, Hafid ^{[1
]}

Ramirez de Arellano, Carmen ^{[2
]}

Bentama, Abdeslem ^{[3
]}

El Hadrami, El Mestafa ^{[3
]}

Julve, Miguel ^{[4
]}

Domingo, Luis R. ^{[2
]}

Stiriba, Salah-Eddine ^{[1
,4
]}

机构：

[1] Univ Cadi Ayyad, Fac Polydisciplinaire Safi, LCAM, Safi 46030, Morocco

[2] Univ Valencia, Dept Quim Organ, Avda Dr Moliner 50, E-46100 Valencia, Spain

[3] Univ Sidi Mohamed Ben Abdellah, Fac Sci & Tech, Lab Chim Organ Appl LCAO, Fes 2202, Morocco

[4] Univ Valencia, Inst Ciencia Mol ICMol, C Catedrat Jose Beltran 2, Valencia 46980, Spain

来源：

CATALYSTS | 2019年 / 9卷 / 08期

关键词：

click chemistry; azides; alkynes; copper(I); poly(pyrazolyl)borate; 1; 2; 3-triazole; DFT calculations; COPPER(I) COMPLEXES; CYCLOADDITION; REACTIVITY; LIGANDS; INDEX;

D O I：

10.3390/catal9080687

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The synthesis of 1,4-disubstituted-1,2,3-triazoles under a copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) regime was accomplished in high yields and a regioselective manner by using two homoscorpionate poly(pyrazolyl)borate anions: tris(pyrazolyl)hydroborate (HB(pz)(3)(-)) and bis(pyrazolyl)hydroborate (H2B(pz)(2)(-)), which stabilized in situ the catalytically active copper (I) center. The [3+2] cycloaddition (32CA) reactions took place under strict click conditions, including room temperature and a mixture of environmentally benign solvents such as water/ethanol in a 1:1 (v/v) ratio. These click chemistry conditions were applied to form complex 1,2,3-triazoles-containing sugar moieties, which are potentially relevant from a biological point of view. Computational modeling carried out by DFT methodologies at the B3LYP/6-31G(d) level showed that the coordination of poly(pyrazolyl)borate-copper(I) to alkyne groups produced relevant changes in terms of generating a high polar copper(I)-acetylide intermediates. The analysis of the global and local reactivity indices explains correctly the role of poly(pyrazolyl)borate ligands in the stabilization and activation of the copper(I) catalyst in the studied 32CA reactions.

引用

页数：17

共 45 条

[1] Copper(II)-dipicolinate-mediated clickable azide-alkyne cycloaddition in water as solvent [J].