Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings

Handle URI:
http://hdl.handle.net/10754/556699
Title:
Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings
Authors:
Wang, Tianli; Yu, Zhaoyuan; Hoon, Ding Long; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Lan, Yu; Lu, Yixin
Abstract:
Phosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)
Citation:
Highly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings 2015 Chem. Sci.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Chem. Sci.
Issue Date:
2-Jun-2015
DOI:
10.1039/C5SC01614B
Type:
Article
ISSN:
2041-6520; 2041-6539
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C5SC01614B
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorWang, Tianlien
dc.contributor.authorYu, Zhaoyuanen
dc.contributor.authorHoon, Ding Longen
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorLan, Yuen
dc.contributor.authorLu, Yixinen
dc.date.accessioned2015-06-10T18:45:35Zen
dc.date.available2015-06-10T18:45:35Zen
dc.date.issued2015-06-02en
dc.identifier.citationHighly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandings 2015 Chem. Sci.en
dc.identifier.issn2041-6520en
dc.identifier.issn2041-6539en
dc.identifier.doi10.1039/C5SC01614Ben
dc.identifier.urihttp://hdl.handle.net/10754/556699en
dc.description.abstractPhosphine-catalyzed highly enantioselective γ-additions of 5H-thiazol-4-ones and 5H-oxazol-4-ones to allenoates have been developed for the first time. With the employment of amino-acid derived bifunctional phosphines, a wide range of substituted 5H-thiazol-4-one and 5H-oxazol-4-one derivatives bearing heteroarom (S or O)-containing tertiary chiral centers were constructed in high yields and excellent enantioselectivities. The reported method provides a facile access to enantioenriched tertiary thioether/alcohols. The mechanism of γ-addition reaction was investigated by performing DFT calculations, and the hydrogen bonding interactions between the Brønsted acid moiety of the phosphine catalysts and the “C=O” unit of donor molecules were shown to be crucial in asymmetric induction.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C5SC01614Ben
dc.rightsArchived with thanks to Chem. Sci. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. http://creativecommons.org/licenses/by/3.0/en
dc.titleHighly Enantioselective Construction of Tertiary Thioethers and Alcohols via Phosphine-Catalyzed Asymmetric γ-Addition reactions of 5H-Thiazol-4-ones and 5H-Oxazol-4-ones: Scope and Mechanistic Understandingsen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalChem. Sci.en
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionDepartment of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore.en
dc.contributor.institutionSchool of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030, P. R. Chinaen
kaust.authorHuang, Kuo-Weien
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