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Article: Catalytic Reductive Desymmetrization of Malonic Esters

TitleCatalytic Reductive Desymmetrization of Malonic Esters
Authors
Issue Date2021
PublisherNature Publishing Group. The Journal's web site is located at http://www.nature.com/nchem/index.html
Citation
Nature Chemistry, 2021, v. 13 n. 7, p. 634-642 How to Cite?
AbstractDesymmetrization of fully substituted carbons with a pair of enantiotopic functional groups is a practical strategy for the synthesis of quaternary stereocentres, as it divides the tasks of enantioselection and C−C bond formation. The use of disubstituted malonic esters as the substrate of desymmetrization is particularly attractive, given their easy and modular preparation, as well as the high synthetic values of the chiral monoester products. Here, we report that a dinuclear zinc complex with a tetradentate ligand can selectively hydrosilylate one of the carbonyls of malonic esters to give α-quaternary β-hydroxyesters, providing a promising alternative to the desymmetric hydrolysis using carboxylesterases. The asymmetric reduction features excellent enantiocontrol that can differentiate sterically similar substituents and high chemoselectivity towards the diester motif of substrates. Together with the versatile preparation of malonic ester substrates and post-reduction derivatization, the desymmetric reduction has enabled the synthesis of a diverse array of quaternary stereocentres with distinct structural features.
Persistent Identifierhttp://hdl.handle.net/10722/300776
ISSN
2023 Impact Factor: 19.2
2023 SCImago Journal Rankings: 6.940
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorXu, P-
dc.contributor.authorHuang, Z-
dc.date.accessioned2021-07-06T03:10:05Z-
dc.date.available2021-07-06T03:10:05Z-
dc.date.issued2021-
dc.identifier.citationNature Chemistry, 2021, v. 13 n. 7, p. 634-642-
dc.identifier.issn1755-4330-
dc.identifier.urihttp://hdl.handle.net/10722/300776-
dc.description.abstractDesymmetrization of fully substituted carbons with a pair of enantiotopic functional groups is a practical strategy for the synthesis of quaternary stereocentres, as it divides the tasks of enantioselection and C−C bond formation. The use of disubstituted malonic esters as the substrate of desymmetrization is particularly attractive, given their easy and modular preparation, as well as the high synthetic values of the chiral monoester products. Here, we report that a dinuclear zinc complex with a tetradentate ligand can selectively hydrosilylate one of the carbonyls of malonic esters to give α-quaternary β-hydroxyesters, providing a promising alternative to the desymmetric hydrolysis using carboxylesterases. The asymmetric reduction features excellent enantiocontrol that can differentiate sterically similar substituents and high chemoselectivity towards the diester motif of substrates. Together with the versatile preparation of malonic ester substrates and post-reduction derivatization, the desymmetric reduction has enabled the synthesis of a diverse array of quaternary stereocentres with distinct structural features.-
dc.languageeng-
dc.publisherNature Publishing Group. The Journal's web site is located at http://www.nature.com/nchem/index.html-
dc.relation.ispartofNature Chemistry-
dc.titleCatalytic Reductive Desymmetrization of Malonic Esters-
dc.typeArticle-
dc.identifier.emailXu, P: pwxu@hku.hk-
dc.identifier.emailHuang, Z: huangzx@hku.hk-
dc.identifier.authorityHuang, Z=rp02585-
dc.description.naturepostprint-
dc.identifier.doi10.1038/s41557-021-00715-0-
dc.identifier.pmid34112991-
dc.identifier.scopuseid_2-s2.0-85107520735-
dc.identifier.hkuros323336-
dc.identifier.volume13-
dc.identifier.issue7-
dc.identifier.spage634-
dc.identifier.epage642-
dc.identifier.isiWOS:000659773500001-
dc.publisher.placeUnited Kingdom-

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