Abstract

A simple protocol to overcome the problematic trifluoromethylation of carbonyl compounds by the potent greenhouse gas “HFC-23, fluoroform” with a potassium base is described. Simply the use of glymes as a solvent or an additive dramatically improves the yields of this transformation. Experimental results and DFT calculations suggest that the beneficial effect deals with glyme coordination to the K+ to produce [K(polyether)n]+ whose diminished Lewis acidity renders the reactive anionoid CF3 counterion species more ‘naked’, thereby slowing down its undesirable decomposition to CF2 and F− and simultaneously increasing its reactivity towards the organic substrate.

Details

Title
Direct nucleophilic trifluoromethylation of carbonyl compounds by potent greenhouse gas, fluoroform: Improving the reactivity of anionoid trifluoromethyl species in glymes
Author
Saito, Takuya 1 ; Wang, Jiandong 1 ; Tokunaga, Etsuko 1 ; Tsuzuki, Seiji 2 ; Shibata, Norio 3   VIAFID ORCID Logo 

1  Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya, Japan 
2  Research Center for Computational Design of Advanced Functional Materials, AIST, Tsukuba, Ibaraki, Japan 
3  Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya, Japan; Institute of Advanced Fluorine-Containing Materials, Zhejiang Normal University, Jinhua, China 
Pages
1-8
Publication year
2018
Publication date
Jul 2018
Publisher
Nature Publishing Group
e-ISSN
20452322
Source type
Scholarly Journal
Language of publication
English
DOI
https://doi.org/10.1038/s41598-018-29748-1
ProQuest document ID
2081312910
Copyright
© 2018. This work is published under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.