title: Transition-Metal-Free Self-Hydrogen-Transferring Allylic Isomerization.
abstract: Phenanthroline and tert-butoxide have been established as powerful radical initiators in reactions such as the SRN1-type coupling reactions due to the cooperation of large heteroarenes and a special feature of tert-butoxide. The first phenanthroline-tert-butoxide-catalyzed transition-metal-free allylic isomerization is described. The resulting ketones are key intermediates for indenes. The control experiments rule out the base-promoted allylic anion pathway. The radical pathway is supported by experimental evidence that includes kinetic study, kinetic isotope effect, isotope-labeling experiments, trapping experiments, and EPR experiments.
authors.affiliation: Center of Advanced Nanocatalysis, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Hong-Xing
authors.initials: HX
authors.lastname: Zheng
authors.affiliation: Center of Advanced Nanocatalysis, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Zu-Feng
authors.initials: ZF
authors.lastname: Xiao
authors.affiliation: Center of Advanced Nanocatalysis, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Chuan-Zhi
authors.initials: CZ
authors.lastname: Yao
authors.affiliation: Center of Advanced Nanocatalysis, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Qiang-Qiang
authors.initials: QQ
authors.lastname: Li
authors.affiliation: Center of Advanced Nanocatalysis, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Xiao-Shan
authors.initials: XS
authors.lastname: Ning
authors.affiliation: Center of Advanced Nanocatalysis, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.
authors.forename: Yan-Biao
authors.initials: YB
authors.lastname: Kang
authors.affiliation: Center of Advanced Nanocatalysis, Department of Chemistry, University of Science and Technology of China , Hefei, Anhui 230026, China.|The State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, CAS , 345 Lingling Lu, Shanghai 200032, China.
authors.forename: Yong
authors.initials: Y
authors.lastname: Tang