Site-Selective α-Alkoxyl Alkynation of Alkyl Esters Mediated by Boryl Radicals
- 29 March 2019
- journal article
- research article
- Published by American Chemical Society (ACS) in Organic Letters
- Vol. 21 (8) , 2927-2931
Abstract
A novel method for site-selective C–H functionalization of ethyl acetate mediated by pyridine–boryl radicals is presented, delivering a variety of 4-phenylbut-3-yn-2-yl acetate derivatives under mild conditions. A distinguishing feature of this reaction is that the pyridine-ligated boryl radicals can abstract the inactive α-hydrogen of the alkoxyl group instead of the α-hydrogen of carbonyl groups described in a previous report using amine-ligated boryl radicals. Significantly, substrates with halogen atoms are compatible under the reaction conditions.Keywords
Funding Information
- National Natural Science Foundation of China (21871100)
- Huazhong University of Science and Technology
- Ministry of Education of the People's Republic of China (2017KFYXJJ166)
- Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica, Huazhong University of Science and Technology (BCMM201805)
This publication has 60 references indexed in Scilit:
- Radical reductions of alkyl halides bearing electron withdrawing groups with N-heterocyclic carbene boranesOrganic & Biomolecular Chemistry, 2011
- N-Heterocyclic carbene-borane radicals as efficient initiating species of photopolymerization reactions under airPolymer Chemistry, 2010
- Radical Deoxygenation of Xanthates and Related Functional Groups with New Minimalist N-Heterocyclic Carbene BoranesOrganic Letters, 2010
- N-Heterocyclic Carbenes−Borane Complexes: A New Class of Initiators for Radical PhotopolymerizationMacromolecules, 2010
- Iridium-Catalyzed α-Alkylation of Acetates with Primary Alcohols and DiolsJournal of the American Chemical Society, 2010
- Linking Borane with N‐Heterocyclic Carbenes: Effective Hydrogen‐Atom Donors for Radical ReactionsAngewandte Chemie International Edition, 2009
- Stable Cyclic (Alkyl)(Amino)Carbenes as Rigid or Flexible, Bulky, Electron‐Rich Ligands for Transition‐Metal Catalysts: A Quaternary Carbon Atom Makes the DifferenceAngewandte Chemie International Edition, 2005
- Polarity-reversal catalysis of hydrogen-atom abstraction reactions: concepts and applications in organic chemistryChemical Society Reviews, 1999
- The effects of β-alkoxy substituents on radical reactions: halogen-atom abstraction from alkyl chloridesJournal of the Chemical Society, Perkin Transactions 2, 1994
- Homolytic reactions of ligated boranes. Part 15. Comparative studies of amine–boranes as donor polarity reversal catalysts for hydrogen-atom abstractionJournal of the Chemical Society, Perkin Transactions 2, 1990