Chemoselective Switch in the Asymmetric Organocatalysis of 5 H -Oxazol-4-ones and N -Itaconimides: Addition-Protonation or [4+2] Cycloaddition

Handle URI:
http://hdl.handle.net/10754/597772
Title:
Chemoselective Switch in the Asymmetric Organocatalysis of 5 H -Oxazol-4-ones and N -Itaconimides: Addition-Protonation or [4+2] Cycloaddition
Authors:
Zhu, Bo; Lee, Richmond; Li, Jiangtao; Ye, Xinyi; Hong, San-Ni; Qiu, Shuai; Coote, Michelle L.; Jiang, Zhiyong
Abstract:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. We report a synthetic strategy for a chemoselective switch and a diastereo-divergent approach for the asymmetric reaction of 5H-oxazol-4-ones and N-itaconimides catalyzed by L-tert-leucine-derived tertiary amine-urea compounds. The reaction was modulated to harness either tandem conjugate addition-protonation or [4+2] cycloaddition as major product with excellent enantio- and diastereoselectivities. Subjecting the enantio-enriched cycloaddition products to a basic silica gel reagent yields the diastereomer vis-à-vis the product directly obtained under conditions for addition-protonation, thus opening a diastereo-divergent route for creating 1,3-tertiary-hetero-quaternary stereocenters. Quantum chemical studies further provide stereochemical analysis for the [4+2] process and a plausible mechanism for this chemoselective switch is proposed.
Citation:
Zhu B, Lee R, Li J, Ye X, Hong S-N, et al. (2015) Chemoselective Switch in the Asymmetric Organocatalysis of 5 H -Oxazol-4-ones and N -Itaconimides: Addition-Protonation or [4+2] Cycloaddition . Angew Chem Int Ed 55: 1299–1303. Available: http://dx.doi.org/10.1002/anie.201507796.
Publisher:
Wiley-Blackwell
Journal:
Angewandte Chemie International Edition
Issue Date:
9-Dec-2015
DOI:
10.1002/anie.201507796
PubMed ID:
26662073
Type:
Article
ISSN:
1433-7851
Sponsors:
Z.J. is grateful for the grants from NSFC (grant number21072044), NCET-11-0938 and the Program for InnovativeResearch Team from the University of Henan Province(14IRTSTHN006). M.L.C. gratefully acknowledges generousallocations of supercomputing time on the National Facility ofthe National Computational Infrastructure, and financialsupport from the Australian Research Council. R.L. alsoacknowledges Dr. Xiaohe Miao (KAUST) for supplementarycomputing time.
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Full metadata record

DC FieldValue Language
dc.contributor.authorZhu, Boen
dc.contributor.authorLee, Richmonden
dc.contributor.authorLi, Jiangtaoen
dc.contributor.authorYe, Xinyien
dc.contributor.authorHong, San-Nien
dc.contributor.authorQiu, Shuaien
dc.contributor.authorCoote, Michelle L.en
dc.contributor.authorJiang, Zhiyongen
dc.date.accessioned2016-02-25T12:56:26Zen
dc.date.available2016-02-25T12:56:26Zen
dc.date.issued2015-12-09en
dc.identifier.citationZhu B, Lee R, Li J, Ye X, Hong S-N, et al. (2015) Chemoselective Switch in the Asymmetric Organocatalysis of 5 H -Oxazol-4-ones and N -Itaconimides: Addition-Protonation or [4+2] Cycloaddition . Angew Chem Int Ed 55: 1299–1303. Available: http://dx.doi.org/10.1002/anie.201507796.en
dc.identifier.issn1433-7851en
dc.identifier.pmid26662073en
dc.identifier.doi10.1002/anie.201507796en
dc.identifier.urihttp://hdl.handle.net/10754/597772en
dc.description.abstract© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. We report a synthetic strategy for a chemoselective switch and a diastereo-divergent approach for the asymmetric reaction of 5H-oxazol-4-ones and N-itaconimides catalyzed by L-tert-leucine-derived tertiary amine-urea compounds. The reaction was modulated to harness either tandem conjugate addition-protonation or [4+2] cycloaddition as major product with excellent enantio- and diastereoselectivities. Subjecting the enantio-enriched cycloaddition products to a basic silica gel reagent yields the diastereomer vis-à-vis the product directly obtained under conditions for addition-protonation, thus opening a diastereo-divergent route for creating 1,3-tertiary-hetero-quaternary stereocenters. Quantum chemical studies further provide stereochemical analysis for the [4+2] process and a plausible mechanism for this chemoselective switch is proposed.en
dc.description.sponsorshipZ.J. is grateful for the grants from NSFC (grant number21072044), NCET-11-0938 and the Program for InnovativeResearch Team from the University of Henan Province(14IRTSTHN006). M.L.C. gratefully acknowledges generousallocations of supercomputing time on the National Facility ofthe National Computational Infrastructure, and financialsupport from the Australian Research Council. R.L. alsoacknowledges Dr. Xiaohe Miao (KAUST) for supplementarycomputing time.en
dc.publisherWiley-Blackwellen
dc.subjectChemoselectivityen
dc.subjectChiralityen
dc.subjectDensity functional calculationsen
dc.subjectOrganocatalysisen
dc.subjectSynthetic methodsen
dc.titleChemoselective Switch in the Asymmetric Organocatalysis of 5 H -Oxazol-4-ones and N -Itaconimides: Addition-Protonation or [4+2] Cycloadditionen
dc.typeArticleen
dc.identifier.journalAngewandte Chemie International Editionen
dc.contributor.institutionKey Laboratory of Natural Medicine and Immuno-Engineering of Henan Province; Henan University; Jinming Campus Kaifeng Henan 475004 P.R. Chinaen
dc.contributor.institutionARC Centre of Excellence for Electromaterials Science, Research School of Chemistry; Australian National University; Canberra ACT 2601 Australiaen
dc.contributor.institutionDivision of Chemistry and Biological Chemistry; Nanyang Technological University; 21 Nanyang Link 637371 Singapore Singaporeen
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