Hydrogenation of fluoroarenes: Direct access to all-cis-(multi)fluorinated cycloalkanes

Mario P. Wiesenfeldt, Zackaria Nairoukh, Wei Li, Frank Glorius*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

160 Scopus citations

Abstract

All-cis-multifluorinated cycloalkanes exhibit intriguing electronic properties. In particular, they display extremely high dipole moments perpendicular to the aliphatic ring, making them highly desired motifs in material science. Very few such motifs have been prepared, as their syntheses require multistep sequences from diastereoselectively prefunctionalized precursors. Herein we report a synthetic strategy to access these valuable materials via the rhodium-cyclic (alkyl)(amino)carbene (CAAC)-catalyzed hydrogenation of readily available fluorinated arenes in hexane. This route enables the scalable single-step preparation of an abundance of multisubstituted and multifluorinated cycloalkanes, including all-cis-1, 2, 3, 4, 5, 6-hexafluorocyclohexane as well as cis-configured fluorinated aliphatic heterocycles.

Original languageAmerican English
Article number908
JournalScience
Volume357
Issue number6354
DOIs
StatePublished - 1 Sep 2017
Externally publishedYes

Bibliographical note

Funding Information:
We gratefully acknowledge the Studienstiftung des Deutschen Volkes (M.P.W.), the Hans-Jensen-Minerva Foundation (Z.N.), the Alexander von Humboldt Foundation (W.L.), and the Deutsche Forschungsgemeinschaft (F.G.) for generous financial support. We thank C. Schlepphorst, L. Candish, M. van Gemmeren, and R. Honeker for helpful discussions. We thank K. Bergander for NMR measurements and helpful discussions and C. G. Daniliuc for x-ray crystallographic analysis. Crystallographic data for 8e and 9e are available free of charge from the Cambridge Crystallographic Data Centre under CCDC-1561951 and CCDC-155388, respectively Additional data are available in the supplementary materials. M.P.W., Z.N., and F.G. are inventors on German patent applicatio 10 2017 106 467.2, held and submitted by Westfälische Wilhelms Universität Münster, which covers a method for the synthesis of fluorinated cyclic aliphatic compounds.

Fingerprint

Dive into the research topics of 'Hydrogenation of fluoroarenes: Direct access to all-cis-(multi)fluorinated cycloalkanes'. Together they form a unique fingerprint.

Cite this