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Cooperative palladium/isothiourea catalyzed enantioselective formal (3+2) cycloaddition of vinylcyclopropanes and α,β-unsaturated esters
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dc.contributor.author | Bitai, Jacqueline | |
dc.contributor.author | Nimmo, Alastair | |
dc.contributor.author | Slawin, Alexandra M. Z. | |
dc.contributor.author | Smith, Andrew D. | |
dc.date.accessioned | 2022-05-03T09:30:45Z | |
dc.date.available | 2022-05-03T09:30:45Z | |
dc.date.issued | 2022-06-20 | |
dc.identifier | 278794356 | |
dc.identifier | aa2c7395-d4ed-4275-a55e-230ed0a314b3 | |
dc.identifier | 85128933445 | |
dc.identifier | 000788376400001 | |
dc.identifier.citation | Bitai , J , Nimmo , A , Slawin , A M Z & Smith , A D 2022 , ' Cooperative palladium/isothiourea catalyzed enantioselective formal (3+2) cycloaddition of vinylcyclopropanes and α,β-unsaturated esters ' , Angewandte Chemie International Edition , vol. 61 , no. 25 , e202202621 . https://doi.org/10.1002/anie.202202621 | en |
dc.identifier.issn | 1433-7851 | |
dc.identifier.other | ORCID: /0000-0002-2104-7313/work/112333090 | |
dc.identifier.other | ORCID: /0000-0002-9527-6418/work/112333135 | |
dc.identifier.uri | https://hdl.handle.net/10023/25270 | |
dc.description | The research leading to these results has received funding from the University of St Andrews (JB) and the EaSI-CAT centre for Doctoral Training (AJN). | en |
dc.description.abstract | A protocol for the enantioselective synthesis of substituted vinylcyclopentanes has been realised using cooperative palladium and isothiourea catalysis. Treatment of vinylcyclopropanes with Pd(PPh3)4 generates a zwitterionic π-allyl palladium intermediate that intercepts a catalytically generated α,β-unsaturated acyl ammonium species prepared from the corresponding α,β-unsaturated para-nitrophenyl ester and the isothiourea (R)-BTM. Intermolecular formal (3+2) cycloaddition between these reactive intermediates generates functionalised cyclopentanes in generally good yields and excellent diastereo- and enantiocontrol (up to >95 : 5 dr, 97 : 3 er), with the use of LiCl as an additive proving essential for optimal stereocontrol. To the best of our knowledge a dual transition metal/organocatalytic process involving α,β-unsaturated acyl ammonium intermediates has not been demonstrated previously. | |
dc.format.extent | 9 | |
dc.format.extent | 6114448 | |
dc.language.iso | eng | |
dc.relation.ispartof | Angewandte Chemie International Edition | en |
dc.subject | α,β-unsaturated acyl ammonium | en |
dc.subject | Palladium catalysis | en |
dc.subject | Isothiourea | en |
dc.subject | Cycloaddition | en |
dc.subject | Cooperative catalysis | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject.lcc | QD | en |
dc.title | Cooperative palladium/isothiourea catalyzed enantioselective formal (3+2) cycloaddition of vinylcyclopropanes and α,β-unsaturated esters | en |
dc.type | Journal article | en |
dc.contributor.sponsor | EPSRC | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | 10.1002/anie.202202621 | |
dc.description.status | Peer reviewed | en |
dc.identifier.grantnumber | EP/L016419/1 | en |
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