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dc.creatorJo, H. H.en_US
dc.creatorGao, X.en_US
dc.creatorYou, L.en_US
dc.creatorAnslyn, E. V.en_US
dc.creatorKrische, M. J.en_US
dc.date.accessioned2016-09-23T18:07:25Z
dc.date.available2016-09-23T18:07:25Z
dc.date.issued2015-08en_US
dc.identifierdoi:10.15781/T2D795C13
dc.identifier.citationJo, H. H., X. Gao, L. You, E. V. Anslyn, and M. J. Krische. "Application of a high-throughput enantiomeric excess optical assay involving a dynamic covalent assembly: parallel asymmetric allylation and ee sensing of homoallylic alcohols." Chemical Science 6, no. 12 (Aug., 2015): 6747-6753.en_US
dc.identifier.issn2041-6520en_US
dc.identifier.urihttp://hdl.handle.net/2152/41161
dc.description.abstractAsymmetric Ir-catalyzed C-C coupling of primary alcohols with allyl-acetates, as described by Krische, to form chiral secondary homo-allylic alcohols were performed in parallel as a means to optimize the ee values thereof. Specifically, approximately 400 examples of this reaction were performed by varying the catalyst, added acids and bases, and starting reactants, to form 4-phenyl-1-butene-4-ol (1). The ee values for the transformations were determined in a high-throughput fashion using a 4-component assembly that creates a circular dichroism signal indicative of the extent of asymmetric induction. Further, a parallel and rapid quantitative TLC method measures the yield of each reaction, revealing which reactions give reliable ee values in the CD-based assay. Overall, the nearly 200 reactions whose ee values were determined could be quantitated in under two hours. Using a combination of the TLC method to measure yield with the CD-assay to measure ee values, several trends in reaction conditions were revealed. For example, it was found that the cyclometalated iridium catalyst modified by BINAP and m-nitro-p-cyano-benzoic acid delivered adduct 1 with the highest levels of enantiomeric enrichment (94%), whereas the corresponding SEGPHOS-modified catalyst gave a comparable yield but lower ee (91%). Most importantly, this study shows that supramolecular assemblies can report hundreds of ee values in a rapid and reliable fashion to analyze parallel synthesis routines.en_US
dc.description.sponsorshipNational Institutes of Health R01GM077437en_US
dc.description.sponsorshipWelch Foundation F-1151en_US
dc.description.sponsorshipNIH RO1-GM069445en_US
dc.language.isoEnglishen_US
dc.relation.ispartofen_US
dc.rightsAdministrative deposit of works to Texas ScholarWorks: This works author(s) is or was a University faculty member, student or staff member; this article is already available through open access or the publisher allows a PDF version of the article to be freely posted online. The library makes the deposit as a matter of fair use (for scholarly, educational, and research purposes), and to preserve the work and further secure public access to the works of the University.en_US
dc.subjectaldehyde oxidation levelen_US
dc.subjectindicator-displacement assaysen_US
dc.subjectcircular-dichroism spectroscopyen_US
dc.subjectforming transfer hydrogenationen_US
dc.subjectcatalyzed carbonyl allylationen_US
dc.subjectthin-layer-chromatographyen_US
dc.subjectrapid-determinationen_US
dc.subjectquantitative-analysisen_US
dc.subjectsecondary alcoholsen_US
dc.subjectchiralen_US
dc.subjectswitchen_US
dc.subjectchemistry, multidisciplinaryen_US
dc.titleApplication of a High-Throughput Enantiomeric Excess Optical Assay Involving a Dynamic Covalent Assembly: Parallel Asymmetric Allylation and ee Sensing of Homoallylic Alcoholsen_US
dc.typeArticleen_US
dc.description.departmentChemistryen_US
dc.rights.restrictionOpenen_US
dc.identifier.doi10.1039/c5sc02416aen_US
dc.contributor.utaustinauthorJo, H. H.en_US
dc.contributor.utaustinauthorGao, X.en_US
dc.contributor.utaustinauthorAnslyn, E. V.en_US
dc.contributor.utaustinauthorKrische, M. J.en_US
dc.relation.ispartofserialChemical Scienceen_US


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