Mechanistic investigation of Rh(i)-catalysed asymmetric Suzuki-Miyaura coupling with racemic allyl halides
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2021Author
van Dijk, LucyArdkhean, Ruchuta
Sidera, Mireia
Karabıyıkoğlu, Sedef
Sari, Özlem
Claridge, Timothy D. W.
Lloyd-Jones, Guy C.
Paton, Robert S.
Fletcher, Stephen P.
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van Dijk, L., Ardkhean, R., Sidera, M., Karabiyikoglu, S., Sari, Ö., Claridge, T. D., ... & Fletcher, S. P. (2021). Mechanistic investigation of Rh (I)-catalysed asymmetric Suzuki–Miyaura coupling with racemic allyl halides. Nature Catalysis, 4(4), 284-292.Abstract
Understanding how catalytic asymmetric reactions with racemic starting materials can operate would enable new enantioselective cross-coupling reactions that give chiral products. Here we propose a catalytic cycle for the highly enantioselective Rh(i)-catalysed Suzuki-Miyaura coupling of boronic acids and racemic allyl halides. Natural abundance C-13 kinetic isotope effects provide quantitative information about the transition-state structures of two key elementary steps in the catalytic cycle, transmetallation and oxidative addition. Experiments with configurationally stable, deuterium-labelled substrates revealed that oxidative addition can happen via syn- or anti-pathways, which control diastereoselectivity. Density functional theory calculations attribute the extremely high enantioselectivity to reductive elimination from a common Rh complex formed from both allyl halide enantiomers. Our conclusions are supported by analysis of the reaction kinetics. These insights into the sequence of bond-forming steps and their transition-state structures will contribute to our understanding of asymmetric Rh-allyl chemistry and enable the discovery and application of asymmetric reactions with racemic substrates.
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Nature CatalysısVolume
4Issue
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