Synthesis of m,n-Diaza[n]helicenes via Skeletal Editing of Indeno[2,1-c]fluorene-5,8-diols

Kód výsledku v 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>

Nalezeny alternativní kódy

RIV/00216208:11310/25:10511776

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Synthesis of m,n-Diaza[n]helicenes via Skeletal Editing of Indeno[2,1-c]fluorene-5,8-diols

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Synthesis of m,n-Diaza[n]helicenes via Skeletal Editing of Indeno[2,1-c]fluorene-5,8-diols

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA25-18076S" target="_blank" >GA25-18076S: Molekulární editace aromatických sloučenin</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

JACS Au

ISSN

2691-3704

e-ISSN

2691-3704

Svazek periodika

5

Číslo periodika v rámci svazku

10

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

4788-4798

Kód UT WoS článku

001587013700001

EID výsledku v databázi Scopus

2-s2.0-105019962267