Controllable Double CF-insertion into Sp C-Cu Bond Using TMSCF: a Facile Access to Tetrafluoroethylene-bridged Structures

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 May 27

PMID 34040722

Citations 4

Authors

Qiqiang Xie

Ziyue Zhu

Lingchun Li

Chuanfa Ni

Jinbo Hu

Affiliations

Soon will be listed here.

Abstract

A highly efficient method for controllable double CF-insertion into pentafluorophenylcopper species using TMSCF as difluoromethylene source has been developed. The newly generated fluoroalkylcopper(i) species, CFCFCFCu, shows good reactivity towards a myriad of structurally diverse aryl, heteroaryl and alkenyl iodides. This protocol is easy to handle, ready to scale up and applicable for the synthesis of relative complex molecules, thus providing a convenient method for facile access to tetrafluoroethylene-bridged structures.

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References

Xie Q, Li L, Zhu Z, Zhang R, Ni C, Hu J . From C to C : TMSCF as a Precursor for Pentafluoroethylation. Angew Chem Int Ed Engl. 2018; 57(40):13211-13215. DOI: 10.1002/anie.201807873. View

Ohashi M, Ishida N, Ando K, Hashimoto Y, Shigaki A, Kikushima K . Cu -Catalyzed Pentafluoroethylation of Aryl Iodides in the Presence of Tetrafluoroethylene and Cesium Fluoride: Determining the Route to the Key Pentafluoroethyl Cu Intermediate. Chemistry. 2018; 24(39):9794-9798. DOI: 10.1002/chem.201802415. View

Berger R, Resnati G, Metrangolo P, Weber E, Hulliger J . Organic fluorine compounds: a great opportunity for enhanced materials properties. Chem Soc Rev. 2011; 40(7):3496-508. DOI: 10.1039/c0cs00221f. View

Liu X, Xu C, Wang M, Liu Q . Trifluoromethyltrimethylsilane: nucleophilic trifluoromethylation and beyond. Chem Rev. 2014; 115(2):683-730. DOI: 10.1021/cr400473a. View

Prakash G, Yudin A . Perfluoroalkylation with Organosilicon Reagents. Chem Rev. 1997; 97(3):757-786. DOI: 10.1021/cr9408991. View

Shirataki H, Ono T, Ohashi M, Ogoshi S . Ni(0)-Catalyzed Three-Component Coupling Reaction of Tetrafluoroethylene and N-Sulfonyl-Substituted Imines with Silanes via Aza-Nickelacycles. Org Lett. 2018; 21(4):851-856. DOI: 10.1021/acs.orglett.8b03674. View

Kirsch P, Bremer M . Understanding fluorine effects in liquid crystals. Chemphyschem. 2009; 11(2):357-60. DOI: 10.1002/cphc.200900745. View

Singh R, Majumder U, Shreeve J . Nucleophilic di- and tetrafluorination of dicarbonyl compounds. J Org Chem. 2001; 66(19):6263-7. DOI: 10.1021/jo0157674. View

Saijo H, Ohashi M, Ogoshi S . Fluoroalkylcopper(I) complexes generated by the carbocupration of tetrafluoroethylene: construction of a tetrafluoroethylene-bridging structure. J Am Chem Soc. 2014; 136(43):15158-61. DOI: 10.1021/ja5093776. View

10.

Kirsch P, Bremer M, Huber F, Lannert H, Ruhl A, Lieb M . Nematic liquid crystals with a tetrafluoroethylene bridge in the mesogenic core structure. J Am Chem Soc. 2001; 123(23):5414-7. DOI: 10.1021/ja010024l. View

11.

Lee G, Harrison D, Korobkov I, Baker R . Stepwise addition of difluorocarbene to a transition metal centre. Chem Commun (Camb). 2013; 50(9):1128-30. DOI: 10.1039/c3cc48468h. View

12.

Li L, Ni C, Xie Q, Hu M, Wang F, Hu J . TMSCF as a Convenient Source of CF =CF for Pentafluoroethylation, (Aryloxy)tetrafluoroethylation, and Tetrafluoroethylation. Angew Chem Int Ed Engl. 2017; 56(33):9971-9975. DOI: 10.1002/anie.201705734. View

13.

Wang F, Luo T, Hu J, Wang Y, Krishnan H, Jog P . Synthesis of gem-difluorinated cyclopropanes and cyclopropenes: trifluoromethyltrimethylsilane as a difluorocarbene source. Angew Chem Int Ed Engl. 2011; 50(31):7153-7. DOI: 10.1002/anie.201101691. View

14.

Kawashima T, Ohashi M, Ogoshi S . Nickel-Catalyzed Formation of 1,3-Dienes via a Highly Selective Cross-Tetramerization of Tetrafluoroethylene, Styrenes, Alkynes, and Ethylene. J Am Chem Soc. 2017; 139(49):17795-17798. DOI: 10.1021/jacs.7b12007. View

15.

Ohashi M, Shirataki H, Kikushima K, Ogoshi S . Nickel-Catalyzed Formation of Fluorine-Containing Ketones via the Selective Cross-Trimerization Reaction of Tetrafluoroethylene, Ethylene, and Aldehydes. J Am Chem Soc. 2015; 137(20):6496-9. DOI: 10.1021/jacs.5b03587. View

16.

Kawashima T, Ohashi M, Ogoshi S . Selective Catalytic Formation of Cross-Tetramers from Tetrafluoroethylene, Ethylene, Alkynes, and Aldehydes via Nickelacycles as Key Reaction Intermediates. J Am Chem Soc. 2018; 140(50):17423-17427. DOI: 10.1021/jacs.8b11671. View

17.

Ohashi M, Adachi T, Ishida N, Kikushima K, Ogoshi S . Synthesis and Reactivity of Fluoroalkyl Copper Complexes by the Oxycupration of Tetrafluoroethylene. Angew Chem Int Ed Engl. 2017; 56(39):11911-11915. DOI: 10.1002/anie.201703923. View