title: Chemoselective reduction and oxidation of ketones in water through control of the electron transfer pathway.
abstract: The selective synthesis of different products from the same starting materials in water, which is the most abundant solvent in nature, is a crucial issue as it maximizes the utilization of materials. Realizing such reactions for ketones is of considerable importance because numerous organic functionalities can be obtained via nucleophilic addition reactions. Herein, we report chemoselective reduction and oxidation reactions of 1,2-diketones in water, which initiates anionic electron transfer from the inorganic electride [Ca24Al28O64](4+)·4e(-), through controlling the pathway of the electrons to substrates. The generation of different radical species for transient intermediates was the key process required to control the reaction selectivity, which was achieved by reacting the anionic electrons with either diketones or O2, leading to the formation of ketyl dianion and superoxide radicals in the reduction and oxidation reactions, respectively. This methodology that utilizes electrides may provide an alternative to the pulse radiolysis of water in synthetic chemistry.
authors.affiliation: Department of Energy Science, Sungkyunkwan University, Suwon 440-746, Republic of Korea.
authors.forename: Sun Min
authors.initials: SM
authors.lastname: Kim
authors.affiliation: 1] Department of Energy Science, Sungkyunkwan University, Suwon 440-746, Republic of Korea [2] IBS Centre for Integrated Nanostructure Physics, Institute for Basic Science, Suwon, Republic of Korea.
authors.forename: Ho Sung
authors.initials: HS
authors.lastname: Yoo
authors.affiliation: 1] Materials Research Center for Element Strategy, Materials and Structures Laboratory, and Frontier Research Center, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan [2] ACCEL Project, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012, Japan.
authors.forename: Hideo
authors.initials: H
authors.lastname: Hosono
authors.affiliation: Department of Energy Science, Sungkyunkwan University, Suwon 440-746, Republic of Korea.
authors.forename: Jung Woon
authors.initials: JW
authors.lastname: Yang
authors.affiliation: 1] Department of Energy Science, Sungkyunkwan University, Suwon 440-746, Republic of Korea [2] IBS Centre for Integrated Nanostructure Physics, Institute for Basic Science, Suwon, Republic of Korea.
authors.forename: Sung Wng
authors.initials: SW
authors.lastname: Kim