A manganese(I)tricarbonyl-catalyst for near room temperature alkene and alkyne hydroarylation Shweta Choudhary, Diego M. Cannas, Matthew Wheatley, and Igor Larrrosa * University of Manchester, UK Transition-metal-catalysed C–H activation is an efficient synthetic tool in organic chemistry to introduce a variety of functionalities in simple to complex molecules. Initially, the method was dominated by expensive, less abundant and highly toxic metals such as rhodium, ruthenium and palladium, however in recent years the studies has expanded over more sustainable, less toxic, and highly abundant environment benign base transition metals. 1 Manganese is 3 rd most abundant transition-metal 2 found in the Earth’s crust, due to its versatile reactivity, low toxicity and high abundance the metal is used to enhance the research field. 3,4 There has been a wealth of literature that discloses advances in the field of Mn-catalysed hydroarylation reactions of C–C multiple bonds, however, these reactions suffer from low catalytic activity due to high temperature conditions (80–100 °C) and high catalyst loadings (commonly 10–20 mol%) (Fig1 a). 5 To overcome these issues we have recently designed a new Mn(I)-tricabonyl complex, MnBr(CO) 3 (MeCN) 2 as catalyst to undergo hydroarylation of alkenes and alkynes at near room temperature (Fig1 c). 6 Our catalyst, MnBr(CO) 3 (MeCN) 2 , enables high-reactivity by providing direct access to active catalytic species (Fig1 b), thereby preventing off-cycle Mn(CO) 4 -species which is responsible for low catalytic activity of commonly used MnBr(CO) 5 . Interestingly, the synthetic pathway was shown to be compatible with various functional groups, including late stage functionalisation and diversification of natural products and pharmaceutical molecules.
References 1. P. Gandeepan,T. Müller,D. Zell,G. Cera,S. WarratzandL. Ackermann, Chem. Rev. , 2019, 119 , 2192 —2452. 2. J. W. Morgan and E. Anders, Proc. Natl. Acad. Sci. U. S. A., 1980, 77 , 6973–6977. 3. D. S. Avila, R. L. Puntel and M. Aschner, Eds.;Springer:Netherlands, Dordrecht,2013,13, 199–227. 4. R. Cano, K. Mackey and G. P. McGlacken, Catal. Sci. Technol. , 2018, 8 , 1251-1266. 5. R. Maayuri and P. Gandeepan, Org. Biomol. Chem. , 2023, 21 , 441-464. 6. S. Choudhary, D. M. Cannas, M. Wheatley and I. Larrosa, Chem. Sci. , 2022, 13 , 13225-13230.
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