Synthesis of m,n-Diaza[n]helicenes via Skeletal Editing of Indeno[2,1-c]fluorene-5,8-diols
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F25%3A00640447" target="_blank" >RIV/61388963:_____/25:00640447 - isvavai.cz</a>
Alternative codes found
RIV/00216208:11310/25:10511776
Result on the web
<a href="https://doi.org/10.1021/jacsau.5c00729" target="_blank" >https://doi.org/10.1021/jacsau.5c00729</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/jacsau.5c00729" target="_blank" >10.1021/jacsau.5c00729</a>
Alternative languages
Result language
angličtina
Original language name
Synthesis of m,n-Diaza[n]helicenes via Skeletal Editing of Indeno[2,1-c]fluorene-5,8-diols
Original language description
Skeletal editing of 5-membered carbocycles to 6-membered heteroaromatic compounds represents an attractive concept that would enable late-stage heteroarene construction. However, the current state of the art does not offer many synthetic strategies on how to achieve such a goal. One of those is based on a reaction of aromatic tertiary alcohols with sodium azide under acidic conditions, i.e., the Schmidt reaction. Herein, we present a hitherto unexplored double Schmidt reaction toward aromatic compounds possessing two pyridine rings. It is the first example of a conversion of 5,8-disubstituted indeno[2,1-c]fluorene-5,8-diols to m,n-diaza[5]helicenes in high yields. We also demonstrate that the regioisomeric ratio can be controlled, to a certain extent, by tuning conditions. Mechanistic investigation encompassing experimental as well as DFT calculations sheds light on the course of the reaction and provides a rationale for the observed regioselectivity and its control. In addition, structures of several diaza[5]helicenes and intermediates were unequivocally confirmed by single crystal X-ray diffraction analyses. The double Schmidt rearrangement strategy was also applied for the transformation of enantioenriched [7]helical indeno[2,1-c]fluorene-5,8-diols into the corresponding enantioenriched m,n-diaza[7]helicenes without significant loss of enantiopurity. Their structures were also unequivocally confirmed by single crystal X-ray diffraction analyses.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10401 - Organic chemistry
Result continuities
Project
<a href="/en/project/GA25-18076S" target="_blank" >GA25-18076S: Molecular Editing of Aromatic Compounds</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2025
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
JACS Au
ISSN
2691-3704
e-ISSN
2691-3704
Volume of the periodical
5
Issue of the periodical within the volume
10
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
4788-4798
UT code for WoS article
001587013700001
EID of the result in the Scopus database
2-s2.0-105019962267