Advanced Search

Show simple item record

dc.contributor.authorvan Dijk, Lucy
dc.contributor.authorArdkhean, Ruchuta
dc.contributor.authorSidera, Mireia
dc.contributor.authorKarabıyıkoğlu, Sedef
dc.contributor.authorSari, Özlem
dc.contributor.authorClaridge, Timothy D. W.
dc.contributor.authorLloyd-Jones, Guy C.
dc.contributor.authorPaton, Robert S.
dc.contributor.authorFletcher, Stephen P.
dc.identifier.citationvan 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.en_US
dc.description.abstractUnderstanding 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.en_US
dc.publisherNature Portfolıoen_US
dc.titleMechanistic investigation of Rh(i)-catalysed asymmetric Suzuki-Miyaura coupling with racemic allyl halidesen_US
dc.relation.journalNature Catalysısen_US
dc.contributor.departmentFen Edebiyat Fakültesien_US
dc.contributor.authorIDÖzlem Sarı / 0000-0002-1000-7500en_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US

Files in this item


This item appears in the following Collection(s)

Show simple item record