Synlett 2016; 27(05): 736-740
DOI: 10.1055/s-0035-1561304
cluster
© Georg Thieme Verlag Stuttgart · New York

Radical Pentafluorosulfanylphenylation of Styrenes by Photoredox Catalysis

Yanjie Li
Chemical Resources Laboratory, Tokyo Institute of Technology, R1-27, 4259 Nagatsuta-cho, Midori-ku, Yokohama, 226-8503, Japan   Email: koike.t.ad@m.titech.ac.jp   Email: makita@res.titech.ac.jp
,
Takashi Koike*
Chemical Resources Laboratory, Tokyo Institute of Technology, R1-27, 4259 Nagatsuta-cho, Midori-ku, Yokohama, 226-8503, Japan   Email: koike.t.ad@m.titech.ac.jp   Email: makita@res.titech.ac.jp
,
Munetaka Akita*
Chemical Resources Laboratory, Tokyo Institute of Technology, R1-27, 4259 Nagatsuta-cho, Midori-ku, Yokohama, 226-8503, Japan   Email: koike.t.ad@m.titech.ac.jp   Email: makita@res.titech.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 23 October 2015

Accepted after revision: 07 December 2015

Publication Date:
05 January 2016 (online)


Abstract

Simple and versatile radical pentafluorosulfanylphenylation (SF5-phenylation) of styrenes by photoredox catalysis has been developed. Pentafluorosulfanylphenyliodonium salts (SF5-phenyliodonium salts), which can be easily prepared from SF5-phenyl iodides and handled without special caution, serve as precursors of SF5-phenyl radicals by action of a ruthenium photoredox catalyst, [Ru(bpy)3]2+. Radical phenylation of styrenes combined with solvolysis or deprotonation leads to a variety of SF5-phenyl-containing compounds via a single step.

Supporting Information

 
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  • 9 Experimental Procedures for the Synthesis of 1a To a stirred solution of pentafluoro(4-iodophenyl)-λ6-sulfane (331 mg, 1.0 mmol) in CH2Cl2–CF3CH2OH (v/v = 1:1, 10.0 mL) was added 69–75 wt% grade of mCPBA (230 mg, 1.0 mmol), followed by addition of TsOH (190 mg, 1.0 mmol). The resulting solution was stirred for 3 h at 40 °C and concentrated under a stream of air, then Et2O (20.0 mL) was added to the residue. The precipitate was filtered and dried in vacuo to afford Koser-type reagent 1′a (459 mg, 89% yield). To a stirred solution of mesitylene (108 mg, 1.0 mmol) in CF3CH2OH (5.0 mL) was added 1′a in one portion at r.t., and the reaction mixture was stirred for 24 h. The mixture was concentrated, and the resulting crude product was precipitated by addition of Et2O. The precipitate was filtered and dried in vacuo to give the product 1a (509 mg, 89%). Recrystallization from MeOH–CH2Cl2 afforded colorless crystals suitable for single-crystal X-ray measurement. Comound 1a: 1H NMR (500 MHz, CD3OD, r.t.): δ = 2.37–2.38 (6 H, Me in mesityl and tosyl), 2.66 (s, 6 H, Me in mesityl), 7.22 (d, J = 7.5 Hz, 2 H, tosyl), 7.29 (s, 2 H, mesityl), 7.70 (d, J = 7.0 Hz, 2 H, tosyl), 7.96 (d, J = 8.0 Hz, 2 H, SF5Ph), 8.05 (d, J = 8.0 Hz, 2 H, SF5Ph). 19F NMR (376 MHz, CD3OD, r.t.): δ = 60.1 (d, J = 148.1 Hz, 4 F), 78.9 (quin, J = 149.5 Hz, 1 F). 13C NMR (125 MHz, CD3OD, r.t.): δ = 21.0 (p-Me in mesityl), 21.3 (Me in tosyl), 27.1 (o-Me in mesityl), 117.5 (mesityl), 122.5 (mesityl), 126.9 (tosyl), 129.8 (tosyl), 130.5 (m, SF5Ph), 131.5 (mesityl), 135.8 (SF5Ph), 141.6 (tosyl), 143.6 (tosyl), 143.7 (SF5Ph), 146.3 (mesityl), 157.1 (apparent t, J = 22.9 Hz, SF5Ph). HRMS (ESI-TOF): m/z calcd for [C15H15F5SI]+: 448.9854; found: 448.9856. For related synthetic method, see: Dohi T., Yamaoka N., Kita Y.; Tetrahedron; 2010, 66: 5775.
  • 10 Compound 1a: CCDC 1431812 contains the supplementary crystallographic data. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.