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. 2017 Jun 2;19(11):2977-2980.
doi: 10.1021/acs.orglett.7b01215. Epub 2017 May 18.

Regio- and Stereoselective Radical Perfluoroalkyltriflation of Alkynes Using Phenyl(perfluoroalkyl)iodonium Triflates

Xi Wang  1 , Armido Studer  1
Affiliations

Regio- and Stereoselective Radical Perfluoroalkyltriflation of Alkynes Using Phenyl(perfluoroalkyl)iodonium Triflates

Xi Wang et al. Org Lett. .

Abstract

A method for regio- and stereoselective anti-addition of the perfluoroalkyl and the triflate group of phenyl(perfluoroalkyl)iodonium triflates to alkynes is presented. The radical reaction uses cheap CuCl as a smart initiator and can be conducted in gram scale. The perfluoroalkyltriflated products are readily further functionalized, rendering this transformation valuable.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Synthesis of Vinyl Perfluoroalkanes
Scheme 2
Scheme 2. Alkyne and I(III)-Reagent Scope,,
Reaction conditions: 1 (0.10 mmol, 1.0 equiv), 2 (0.17 mmol, 1.7 equiv), CuCl (0.01 mmol, 10 mol %), DCM (1 mL), 45 °C, 15 h. Isolated yield. E/Z isomer ratio determined by 19F NMR analysis and GC-MS analysis on the crude product. Unless noted otherwise, E/Z > 20:1. 1 (0.10 mmol, 1.0 equiv), 2 (0.15 mmol, 1.5 equiv), CuCl (0.01 mmol, 10 mol %), and DCM (1 mL), room temperature, 24 h. After 15 h, renewed CuCl (0.01 mmol, 10 mol %), 2 (0.17 mmol, 1.7 equiv), and DCM (1 mL) addition and continued stirring at 45 °C for another 15 h. After 24 h, renewed CuCl (0.01 mmol, 10 mol %), 2 (0.15 mmol, 1.5 equiv), and DCM (1 mL) addition and continued stirring at room temperature for another 24 h. Yield determined by 19F NMR analysis using PhCF3 as an internal standard. E:Z = 17:1.
Scheme 3
Scheme 3. Further Functionalization of Perfluoroalkyltriflated Products
Scheme 4
Scheme 4. Suggested Mechanism
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