title: Oxydifluoromethylation of Alkenes by Photoredox Catalysis: Simple Synthesis of CF2H-Containing Alcohols.
abstract: We have developed a novel and simple protocol for the direct incorporation of a difluoromethyl (CF2 H) group into alkenes by visible-light-driven photoredox catalysis. The use of fac-[Ir(ppy)3] (ppy=2-pyridylphenyl) photocatalyst and shelf-stable Hu's reagent, N-tosyl-S-difluoromethyl-S-phenylsulfoximine, as a CF2 H source is the key to success. The well-designed photoredox system achieves synthesis of not only β-CF2 H-substituted alcohols but also ethers and an ester from alkenes through solvolytic processes. The present method allows a single-step and regioselective formation of C(sp(3))-CF2 H and C(sp(3))-O bonds from C=C moiety in alkenes, such as hydroxydifluoromethylation, regardless of terminal or internal alkenes. Moreover, this methodology tolerates a variety of functional groups.
authors.affiliation: Chemical Resources Laboratory, Tokyo Institute of Technology, R1-27, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
authors.forename: Yusuke
authors.initials: Y
authors.lastname: Arai
authors.affiliation: Chemical Resources Laboratory, Tokyo Institute of Technology, R1-27, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
authors.forename: Ren
authors.initials: R
authors.lastname: Tomita
authors.affiliation: Chemical Resources Laboratory, Tokyo Institute of Technology, R1-27, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan.
authors.forename: Gaku
authors.initials: G
authors.lastname: Ando
authors.affiliation: Chemical Resources Laboratory, Tokyo Institute of Technology, R1-27, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan. koike.t.ad@m.titech.ac.jp.
authors.forename: Takashi
authors.identifier: http://orcid.org/0000-0002-3737-7093
authors.initials: T
authors.lastname: Koike
authors.affiliation: Chemical Resources Laboratory, Tokyo Institute of Technology, R1-27, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan. makita@res.titech.ac.jp.
authors.forename: Munetaka
authors.identifier: http://orcid.org/0000-0001-7007-9621
authors.initials: M
authors.lastname: Akita
keywords: alcohols; fluorine; homogeneous catalysis; iridium; photochemistry