Sterically controlled isodesmic late-stage C–H iodination of arenes Mirxan Farizyan 1 , Rita de Jesus +,2 , Jyotirmoy Dey +,2 , Manuel van Gemmeren* 1,2 1 Organisch-Chemisches Institut, Westfalische Wilhelms-Universitat Munster, Germany; 2 Otto-Diels-Institut für Organische Chemie, Christian-Albrechts-Universität zu Kiel, Germany; + These authors contributed equally to this work Aryl iodides are versatile precursors for the synthesis of pharmaceuticals and agrochemicals. [1] Several synthetic methodologies can be applied to generate these molecules, such as electrophilic aromatic substitution (S E Ar), [2] or via prefunctionalized starting materials (e.g. Sandmeyer reaction). [3] The direct conversion of C–H bonds into C–I bonds with a sterically controlled regioselectivity, would be complementary to these (electronically controlled) methods and would reduce functional group interconversions. Inspired by recent work on isodesmic functional group metathesis, [4] we developed a dual ligand based palladium catalyst for the nondirected C–H activation of arenes under steric control. [5] The high functional group tolerance, reflected in a broad substrate scope, renders this method useful for late stage functionalization.
Scheme 1 : Sterically controlled C–H/C–I metathesis using a dual ligand palladium catalyst. References 1. K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angewandte Chemie International Edition 2005 , 44 , 4442. 2. R. Taylor, Electrophilic Aromatic Substitution , Wiley, 1990 . 3. H. H. Hodgson, Chem. Rev. 1947 , 40 , 251.
4. a) Y. H. Lee, B. Morandi, Nature Chemistry 2018 , 10 , 1016; b) M. De La Higuera Macias, B. A. Arndtsen, J. Am. Chem. Soc. 2018 , 140 , 10140; c) N. Wang, Z. Chi, X. Wang, Z. Gao, S. Li, G. Li, Org. Lett. 2022 , 24 , 3657; d) Z. Gao, H. Wang, C. Zhou, N. Wang, S. Li, G. Li, Org. Lett. 2022 , 24 , 3926; e) S. Li, C. Zhang, L. Fu, H. Wang, L. Cai, X. Chen, X. Wang, G. Li, CCS Chemistry 2021 , 4 , 1889. 5. M. Farizyan, R. de Jesus, J. Dey, M. van Gemmeren, Chem. Sci. 2023 , 14 , 4357.
P26F
© The Author(s), 2023
Made with FlippingBook Learn more on our blog