Baral Ek Raj, Lee Jun Hee, Kim Jeung Gon
Department of Chemistry and Research Institute of Physics and Chemistry , Chonbuk National University , Jeonju 54896 , Republic of Korea.
Department of Advanced Materials Chemistry , Dongguk University , Gyeongju 38066 , Republic of Korea.
J Org Chem. 2018 Oct 5;83(19):11768-11776. doi: 10.1021/acs.joc.8b01695. Epub 2018 Sep 18.
A practical, safe, and highly efficient carbonylation system involving a diphenyl carbonate, an organocatalyst, and various diols is presented herein and produces highly valuable cyclic carbonates. In reactions with a wide range of diols, diphenyl carbonate was activated by bicyclic guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst, which successfully replaced highly toxic and unstable phosgene or its derivatives while maintaining the desired high reactivity. Moreover, this new system can be used to synthesize sterically demanding cyclic carbonates such as tetrasubstituted pinacol carbonates, which are not accessible via other conventional methods.
本文介绍了一种实用、安全且高效的羰基化体系，该体系涉及碳酸二苯酯、有机催化剂和各种二醇，可生产高价值的环状碳酸酯。在与多种二醇的反应中，碳酸二苯酯由双环胍1,5,7-三氮杂双环[4.4.0]癸-5-烯（TBD）作为催化剂进行活化，该催化剂成功替代了剧毒且不稳定的光气或其衍生物，同时保持了所需的高反应活性。此外，这种新体系可用于合成空间位阻较大的环状碳酸酯，如四取代频哪醇碳酸酯，而这些是其他传统方法无法获得的。
