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Understanding divergent substrate stereoselectivity in the isothiourea-catalysed conjugate addition of cyclic α-substituted β-ketoesters to α,β-unsaturated aryl esters
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dc.contributor.author | Yuan, Ding | |
dc.contributor.author | Goodfellow, Alister S. | |
dc.contributor.author | Duan, Zhuan | |
dc.contributor.author | Kang, Tengfei | |
dc.contributor.author | Kasten, Kevin | |
dc.contributor.author | Cordes, David B. | |
dc.contributor.author | McKay, Aidan | |
dc.contributor.author | Buehl, Michael | |
dc.contributor.author | Boyce, Gregory R. | |
dc.contributor.author | Smith, Andrew D. | |
dc.date.accessioned | 2023-12-06T13:30:01Z | |
dc.date.available | 2023-12-06T13:30:01Z | |
dc.date.issued | 2023-12-28 | |
dc.identifier | 296736644 | |
dc.identifier | 936ccee5-dc90-4ebc-b4a7-f1f78f61acc0 | |
dc.identifier | 85179152614 | |
dc.identifier.citation | Yuan , D , Goodfellow , A S , Duan , Z , Kang , T , Kasten , K , Cordes , D B , McKay , A , Buehl , M , Boyce , G R & Smith , A D 2023 , ' Understanding divergent substrate stereoselectivity in the isothiourea-catalysed conjugate addition of cyclic α-substituted β-ketoesters to α,β-unsaturated aryl esters ' , Chemical Science , vol. 14 , no. 48 , pp. 14146-14156 . https://doi.org/10.1039/D3SC05470E | en |
dc.identifier.issn | 2041-6520 | |
dc.identifier.other | ORCID: /0000-0002-1095-7143/work/147967096 | |
dc.identifier.other | ORCID: /0000-0002-5366-9168/work/147967115 | |
dc.identifier.other | ORCID: /0000-0002-2104-7313/work/147967336 | |
dc.identifier.uri | https://hdl.handle.net/10023/28822 | |
dc.description | The research leading to these results has received funding from the CSC (DY), the EPSRC (TK, KK, EP/T023643/1) and the EaSI-CAT centre for Doctoral Training (ASG). ADS thanks the EPSRC Programme Grant “Boron: Beyond the Reagent” (EP/W007517) for support. | en |
dc.description.abstract | The development of enantioselective synthetic methods capable of generating vicinal stereogenic centres, where one is tetrasubstituted (such as either an all-carbon quaternary centre or where one or more substituents are heteroatoms), is a recognised synthetic challenge. Herein, the enantioselective conjugate addition of a range of carbo- and heterocyclic α-substituted β-keto esters to α,β-unsaturated aryl esters using the isothiourea HyperBTM as a Lewis base catalyst is demonstrated. Notably, divergent diastereoselectivity is observed through the use of either cyclopentanone-derived or indanone-derived substituted β-keto esters with both generating the desired stereodefined products with high selectivity (>95:5 dr, up to 99:1 er). The scope and limitations of these processes are demonstrated, alongside application on gram scale. The origin of the divergent substrate selectivity has been probed through the use of DFT-analysis, with preferential orientation driven by dual stabilising CH···O interactions. The importance of solvation with strongly polar transition-states is highlighted and the SMD (Solvent Model Density) is demonstrated to capture solvation effects reliably. | |
dc.format.extent | 11 | |
dc.format.extent | 2740564 | |
dc.language.iso | eng | |
dc.relation.ispartof | Chemical Science | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject.lcc | QD | en |
dc.title | Understanding divergent substrate stereoselectivity in the isothiourea-catalysed conjugate addition of cyclic α-substituted β-ketoesters to α,β-unsaturated aryl esters | en |
dc.type | Journal article | en |
dc.contributor.sponsor | EPSRC | en |
dc.contributor.sponsor | UK Research and Innovation | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | https://doi.org/10.1039/D3SC05470E | |
dc.description.status | Peer reviewed | en |
dc.identifier.grantnumber | EP/T023643/1 | en |
dc.identifier.grantnumber | EP/W007517/1 | en |
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