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Isolation and characterization of (Ar)(F)B(OR)2Cs and (PN)CuAr complexes. Involvement of cationic copper(I) species during transmetalation of arylboron reagents with (PN)CuF
Affiliation:1. Department of Chemistry, Bapatla Engineering College, Bapatla, Guntur, AP, 522101, India;2. Department of Chemistry, Gudlavalleru Engineering College, Gudlavalleru, Krishna, AP, India;3. Department of Chemistry, GITAM University, NH-207, Doddaballapur Taluk, Bengaluru District, Karnataka 561203, India;1. School of Chemical Sciences, University of Chinese Academy of Sciences, No. 19A, Yuquan Road, Beijing, 100049, PR China;2. College of Earth and Planetary Sciences, University of Chinese Academy of Sciences, Key Laboratory of Computational Geodynamics, Chinese Academy of Sciences, Beijing, 100049, PR China;1. The College of Chemistry and Molecular Engineering, Henan Key Laboratory of Chemical Biology and Organic, Key Laboratory of Applied Chemistry of Henan Universities, Zhengzhou University, Zhengzhou, Henan, 450052, PR China;2. TetranovBiopharm, LLC. &Collaborative Innovation Center of New Drug Research and Safety Evaluation, Zhengzhou, Henan, 450001, PR China;1. EaStCHEM, School of Chemistry, University of St Andrews, Purdie Building, North Haugh, St Andrews KY16 9ST United Kingdom;2. van ''t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam, the Netherlands;3. Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany
Abstract:We report the synthesis and characterization of novel anionic arylfluoroborate, three-coordinate ligated arylcopper(I) and cationic ligated copper(I) complexes. We show through in situ 19F NMR monitoring that neutral arylboronate ester is more kinetically competent than anionic arylfluoroborate for transmetalation with (PN)CuF (PN = o-(di-tert-butylphosphino)-N,N-dimethylaniline). The transmetalation of the neutral arylboronate ester proceeds via a two-step process involving a cationic copper(I) species wherein an anionic arylfluoroborate is generated in situ as a competent aryl group transferring reagent.
Keywords:arylboronate  Arylcopper(I)  Arylfluoroboronate  Cationic  Transmetalation
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