Organocatalytic Coupling of CO2 with a Propargylic Alcohol: A Comprehensive Mechanistic Study

被引：29
作者：
Boyaval, Amelie [1 ,2 ]
Mereau, Raphael [1 ]
Grignard, Bruno [2 ]
Detrembleur, Christophe [2 ]
Jerome, Christine [2 ]
Tassaing, Thierry [1 ]
机构：
[1] Univ Bordeaux, CNRS, ISM, UMR5255, 351 Cours Liberat, F-33405 Talence, France
[2] Univ Liege, Dept Chem, CERM, B6a,Allee 6 Aout, B-4000 Liege, Belgium
来源：
CHEMSUSCHEM | 2017年 / 10卷 / 06期
关键词：
bicyclic guanidine; DFT calculations; carbon dioxide; organocatalysis; alpha-methylene carbonate; CARBON-DIOXIDE; CYCLIC CARBONATES; CARBOXYLATIVE CYCLIZATION; CATALYZED SYNTHESIS; CONVERSION; ACTIVATION; TRANSFORMATION; EPOXIDES; FIXATION;
D O I：
10.1002/cssc.201601524
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The metal-free coupling of a propargylic alcohol with CO2 catalysed by guanidine derivatives was investigated in detail through the combination of online kinetic studies by insitu attenuated-total reflection IR (ATR-IR) spectroscopy and DFT calculations. Bicyclic guanidines, namely 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) are effective catalysts for the conversion of 2-methyl-3-butyn-2-ol to -methylene cyclic carbonate and oxoalkyl acyclic carbonate under mild reaction conditions. The lower selectivity of TBD in comparison with MTBD towards the formation of -methylene cyclic carbonate was elucidated from DFT calculations and is related to the bifunctional activity (base/H-bond donor) of TBD decreasing the Gibbs free energy of the reaction path for the formation of the acyclic carbonate.
引用
收藏
页码：1241 / 1248
页数：8
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