There is a newer version of the archive available

Data for all-Oxygen Carbon Stereocenters: Synthesis, Enantiomeric Stability, Resolution and Absolute Configuration

Stereogenic atoms represent one of the most fundamental forms of molecular chirality. Despite decades of research, certain atomic assemblies remain unknown as single enantiomers, such as tetra heterosubstituted methanes. Herein, a one-step strategy to chiral all-oxygen spiro adducts is reported. Using enantioselective dynamic chromatography, a remarkable barrier of enantiomerization is determined (DeltaG‡298 up to 27.6 kcal/mol). Single enantiomers are afforded by chiral stationary phase high-performance liquid chromatography. A cryptochiral character (gabs ~10-5) is revealed by electronic circular dichroism analysis affording nevertheless robust absolute configuration assignment by TDDFT calculations. Crystalline diastereomeric structures made from rigid pinane skeletons confirm the structural and configurational assignments. Our study highlights that tetraoxa carbon (stereo)centers are readily made and isolated, and constitute possible targets for new (asymmetric) functional group manipulations.

Organizational unit: Laboratory of Professor Jérôme Lacour

Type: Dataset

DOI: 10.26037/yareta:uaqqxl3mzvhotoihpqbruxieda

Rendered obsolete by the following DOI

License: Creative Commons Attribution 4.0 International

Publication date

09/12/2024

Retention date07/12/2034

Access levelPublic

SensitivityBlue

Contract on the use of data

License

Contributors

Viudes, Olivier

Besnard, Céline

Siegle, Alexander F.

Trapp, Oliver

Bürgi, Thomas

Pescitelli, Gennaro

Lacour, Jérôme

Files

1393 Files (293.1 MB)

Quality (0 Reviews)
Usefulness (0 Reviews)

    
      <?xml version="1.0" encoding="UTF-8" standalone="yes"?>
<datacite:resource xmlns:premis="http://www.loc.gov/premis/v3" xmlns:mets="http://www.loc.gov/METS/" xmlns:datacite="http://datacite.org/schema/kernel-4" xmlns:dlcm="http://www.dlcm.ch/dlcm/v2" xmlns:fits="http://hul.harvard.edu/ois/xml/ns/fits/fits_output" xmlns:xlink="http://www.w3.org/1999/xlink">
    <datacite:identifier identifierType="DOI">10.26037/yareta:uaqqxl3mzvhotoihpqbruxieda</datacite:identifier>
    <datacite:creators>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Viudes, Olivier</datacite:creatorName>
            <datacite:givenName>Olivier</datacite:givenName>
            <datacite:familyName>Viudes</datacite:familyName>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Besnard, Céline</datacite:creatorName>
            <datacite:givenName>Céline</datacite:givenName>
            <datacite:familyName>Besnard</datacite:familyName>
            <datacite:nameIdentifier xsi:type="datacite:nameIdentifier" nameIdentifierScheme="ORCID" schemeURI="https://orcid.org/" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">0000-0001-5699-9675</datacite:nameIdentifier>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Siegle, Alexander F.</datacite:creatorName>
            <datacite:givenName>Alexander F.</datacite:givenName>
            <datacite:familyName>Siegle</datacite:familyName>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Trapp, Oliver</datacite:creatorName>
            <datacite:givenName>Oliver</datacite:givenName>
            <datacite:familyName>Trapp</datacite:familyName>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Bürgi, Thomas</datacite:creatorName>
            <datacite:givenName>Thomas</datacite:givenName>
            <datacite:familyName>Bürgi</datacite:familyName>
            <datacite:nameIdentifier xsi:type="datacite:nameIdentifier" nameIdentifierScheme="ORCID" schemeURI="https://orcid.org/" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">0000-0003-0906-082X</datacite:nameIdentifier>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Pescitelli, Gennaro</datacite:creatorName>
            <datacite:givenName>Gennaro</datacite:givenName>
            <datacite:familyName>Pescitelli</datacite:familyName>
        </datacite:creator>
        <datacite:creator>
            <datacite:creatorName nameType="Personal">Lacour, Jérôme</datacite:creatorName>
            <datacite:givenName>Jérôme</datacite:givenName>
            <datacite:familyName>Lacour</datacite:familyName>
            <datacite:nameIdentifier xsi:type="datacite:nameIdentifier" nameIdentifierScheme="ORCID" schemeURI="https://orcid.org/" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">0000-0001-6247-8059</datacite:nameIdentifier>
        </datacite:creator>
    </datacite:creators>
    <datacite:titles>
        <datacite:title>Data for all-Oxygen Carbon Stereocenters: Synthesis, Enantiomeric Stability, Resolution and Absolute Configuration</datacite:title>
    </datacite:titles>
    <datacite:publisher>Université de Genève, Yareta</datacite:publisher>
    <datacite:publicationYear>2024</datacite:publicationYear>
    <datacite:resourceType resourceTypeGeneral="Dataset">Dataset</datacite:resourceType>
    <datacite:contributors>
        <datacite:contributor contributorType="ResearchGroup">
            <datacite:contributorName nameType="Organizational">[acac4008-69e9-45cf-ac63-a1752ec63ade] Laboratory of Professor Jérôme Lacour</datacite:contributorName>
            <datacite:affiliation xsi:type="datacite:affiliation" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">[UNIGE-Sciences] Université de Genève - Faculté des Sciences</datacite:affiliation>
            <datacite:affiliation xsi:type="datacite:affiliation" affiliationIdentifier="https://ror.org/01swzsf04" affiliationIdentifierScheme="ROR" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance">[UNIGE] Université de Genève</datacite:affiliation>
        </datacite:contributor>
        <datacite:contributor contributorType="ProjectManager">
            <datacite:contributorName nameType="Personal">Cazeaux, Hugues</datacite:contributorName>
        </datacite:contributor>
        <datacite:contributor contributorType="ProjectManager">
            <datacite:contributorName nameType="Personal">Lacour, Jérôme</datacite:contributorName>
        </datacite:contributor>
    </datacite:contributors>
    <datacite:dates>
        <datacite:date dateType="Issued">2024-12-09T00:00:00Z</datacite:date>
        <datacite:date dateType="Created">2024-12-09T11:00:55.497121Z</datacite:date>
        <datacite:date dateType="Updated">2025-05-20T04:55:16.285632Z</datacite:date>
        <datacite:date dateType="Accepted">2024-12-10T13:54:30.979072007Z</datacite:date>
    </datacite:dates>
    <datacite:alternateIdentifiers>
        <datacite:alternateIdentifier alternateIdentifierType="ARK">ark:/64642/rt9uaqqxl3mzvhotoihpqbruxieda</datacite:alternateIdentifier>
    </datacite:alternateIdentifiers>
    <datacite:relatedIdentifiers>
        <datacite:relatedIdentifier relatedIdentifierType="DOI" relationType="IsObsoletedBy">10.26037/yareta:26l4n6rn5bgovfx45rlfedw4ou</datacite:relatedIdentifier>
    </datacite:relatedIdentifiers>
    <datacite:formats>
        <datacite:format>application/octet-stream</datacite:format>
        <datacite:format>text/csv</datacite:format>
        <datacite:format>text/plain</datacite:format>
        <datacite:format>application/x-dosexec</datacite:format>
        <datacite:format>inode/x-empty</datacite:format>
        <datacite:format>application/rtf</datacite:format>
        <datacite:format>application/vnd.ms-excel</datacite:format>
        <datacite:format>application/vnd.openxmlformats-officedocument.spreadsheetml.sheet</datacite:format>
        <datacite:format>text/xml</datacite:format>
        <datacite:format>application/pdf</datacite:format>
        <datacite:format>audio/mpeg</datacite:format>
        <datacite:format>image/png</datacite:format>
        <datacite:format>application/vnd.openxmlformats-officedocument.wordprocessingml.document</datacite:format>
        <datacite:format>application/x-sqlite3</datacite:format>
        <datacite:format>text/html</datacite:format>
    </datacite:formats>
    <datacite:rightsList>
        <datacite:rights rightsURI="https://www.dlcm.ch/access-level/final">PUBLIC</datacite:rights>
        <datacite:rights rightsURI="https://www.dlcm.ch/data-tag">BLUE</datacite:rights>
        <datacite:rights rightsURI="https://creativecommons.org/licenses/by/4.0/" rightsIdentifier="CC-BY-4.0" rightsIdentifierScheme="SPDX">Creative Commons Attribution 4.0 International</datacite:rights>
        <datacite:rights rightsURI="https://creativecommons.org/licenses/by/4.0/" rightsIdentifier="CC-BY-4.0" rightsIdentifierScheme="SPDX">Creative Commons Attribution 4.0 International</datacite:rights>
        <datacite:rights rightsURI="https://www.dlcm.ch/data-use-policy">LICENSE</datacite:rights>
    </datacite:rightsList>
    <datacite:descriptions>
        <datacite:description descriptionType="Abstract">Stereogenic atoms represent one of the most fundamental forms of molecular chirality. Despite decades of research, certain atomic assemblies remain unknown as single enantiomers, such as tetra heterosubstituted methanes. Herein, a one-step strategy to chiral all-oxygen spiro adducts is reported. Using enantioselective dynamic chromatography, a remarkable barrier of enantiomerization is determined (DeltaG‡298 up to 27.6 kcal/mol). Single enantiomers are afforded by chiral stationary phase high-performance liquid chromatography. A cryptochiral character (gabs ~10-5) is revealed by electronic circular dichroism analysis affording nevertheless robust absolute configuration assignment by TDDFT calculations. Crystalline diastereomeric structures made from rigid pinane skeletons confirm the structural and configurational assignments. Our study highlights that tetraoxa carbon (stereo)centers are readily made and isolated, and constitute possible targets for new (asymmetric) functional group manipulations.</datacite:description>
    </datacite:descriptions>
    <datacite:fundingReferences/>
</datacite:resource>