New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration
Harford, Philip J
Royal Society of Chemistry
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Harford, P. J., Peel, A., Chevallier, F., Takita, R., Mongin, F., Uchiyama, M., & Wheatley, A. (2014). New avenues in the directed deprotometallation of aromatics: recent advances in directed cupration. Dalton Transactions https://doi.org/10.1039/C4DT01130A
Recent advances in the selective deprotometallation of aromatic reagents using alkali metal cuprates are reported. The ability of these synergic bases to achieve efficient deprotonation under the influence of a directing group is explored in the context of achieving new and more efficient organic transformations whilst encouraging greater ancillary group tolerance by the base. Developments in our understanding of the structural chemistry of alkali metal cuprates are reported, with both Gilman cuprates of the type R2CuLi and Lipshutz and related cuprates of the type R2Cu(X)Li2 (X = inorganic anion) elucidated and rationalised in terms of ligand sterics. The generation of new types of cuprate motif are introduced through the development of adducts between different classes of cuprate. The use of DFT methods to interrogate the mechanistic pathways towards deprotonative metallation is described. Theoretical modelling of in situ rearrangements undergone by the cuprate base are discussed, with a view to understanding the relationship between R2CuLi and R2Cu(X)Li2, their interconversion and the implications of this for cuprate reactivity. The advent of a new class of adduct between different cuprate types is developed and interpreted in terms of the options for expelling LiX from R2Cu(X)Li2. Applications in the field of medicinal chemistry and (hetero)arene derivatization are explored.
Much of this work was supported by the U.K. EPSRC (EP/J500380/1). A.W. would like to acknowledge the graduate students who have contributed to the work in the past (Drs. James Morey and Joanna Haywood) and also the GB Sasakawa and Daiwa Foundations and the Royal Society for support with travel and international collaboration. A.W. and M.U. thank the Japan Society for the Promotion of Science. M.U. acknowledges the personnel who have contributed to the work (Yuichi Hashimoto, Yotaro Matsumoto and Keiichi Hirano, Drs. Shinsuke Komagawa, Shinya Usui and Ching-Yuan Liu, and Professors Shuji Yasuike and Jyoji Kurita). M.U. also thanks Hoansha and KAKENHI (Young Scientist (A), Houga, and Priority Area No. 452 and 459), the Daiichi-Sankyo, Asahi Glass, Mitsubishi, Uehara Memorial, Takeda Science, Sumimoto and NAGASE Science and Technology Foundations. F.C. and F.M. would like to acknowledge the graduate students who have contributed to the work (Dr. Tan Tai Nguyen and Ms. Nada Marquise) and the Agence Nationale de la Recherche (ACTIVATE program) for financial support. F.M. also thanks the Institut Universitaire de France and Rennes Métropole.
External DOI: https://doi.org/10.1039/C4DT01130A
This record's URL: https://www.repository.cam.ac.uk/handle/1810/245403