Please use this identifier to cite or link to this item: https://hdl.handle.net/10356/137033
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dc.contributor.authorCui, Xi-Yangen_US
dc.contributor.authorGe, Yicenen_US
dc.contributor.authorTan, Siu Minen_US
dc.contributor.authorJiang, Huanen_US
dc.contributor.authorTan, Davinen_US
dc.contributor.authorLu, Yunpengen_US
dc.contributor.authorLee, Richmonden_US
dc.contributor.authorTan, Choon-Hongen_US
dc.date.accessioned2020-02-13T06:11:54Z-
dc.date.available2020-02-13T06:11:54Z-
dc.date.issued2018-
dc.identifier.citationCui, X.-Y., Ge, Y., Tan, S. M., Jiang, H., Tan, D., Lu, Y., . . . Tan, C.-H. (2018). (Guanidine) copper complex-catalyzed enantioselective dynamic kinetic allylic alkynylation under biphasic condition. Journal of The American Chemical Society, 140(27), 8448-8455. doi:10.1021/jacs.7b12806en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttps://hdl.handle.net/10356/137033-
dc.description.abstractHighly enantioselective allylic alkynylation of racemic bromides under biphasic condition is furnished in this report. This approach employs functionalized terminal alkynes as pro-nucleophiles and provides 6- and 7-membered cyclic 1,4-enynes with high yields and excellent enantioselectivities (up to 96% ee) under mild conditions. Enantioretentive derivatizations highlight the synthetic utility of this transformation. Cold-spray ionization mass spectrometry (CSI-MS) and X-ray crystallography were used to identify some catalytic intermediates, which include guanidinium cuprate ion pairs and a copper-alkynide complex. A linear correlation between the enantiopurity of the catalyst and reaction product indicates the presence of a copper complex bearing a single guanidine ligand at the enantio-determining step. Further experimental and computational studies supported that the alkynylation of allylic bromide underwent an anti-SN2' pathway catalyzed by nucleophilic cuprate species. Moreover, metal-assisted racemization of allylic bromide allowed the reaction to proceed in a dynamic kinetic fashion to afford the major enantiomer in high yield.en_US
dc.language.isoenen_US
dc.relation.ispartofJournal of the American Chemical Societyen_US
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.7b12806en_US
dc.subjectScience::Chemistryen_US
dc.title(Guanidine) copper complex-catalyzed enantioselective dynamic kinetic allylic alkynylation under biphasic conditionen_US
dc.typeJournal Articleen
dc.contributor.schoolSchool of Physical and Mathematical Sciencesen_US
dc.identifier.doi10.1021/jacs.7b12806-
dc.description.versionAccepted versionen_US
dc.identifier.pmid29894179-
dc.identifier.scopus2-s2.0-85048700509-
dc.identifier.issue27en_US
dc.identifier.volume140en_US
dc.identifier.spage8448en_US
dc.identifier.epage8455en_US
dc.subject.keywordsGuanidineen_US
dc.subject.keywordsAnionsen_US
item.grantfulltextopen-
item.fulltextWith Fulltext-
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