Chemistry of 2,14-Dithiacalix[4]arene: Searching for the Missing Fifth Conformer

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F21%3A43923435" target="_blank" >RIV/60461373:22310/21:43923435 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22810/21:43923435

Výsledek na webu

<a href="https://pubs.acs.org/doi/pdf/10.1021/acs.joc.1c01173" target="_blank" >https://pubs.acs.org/doi/pdf/10.1021/acs.joc.1c01173</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.joc.1c01173" target="_blank" >10.1021/acs.joc.1c01173</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Chemistry of 2,14-Dithiacalix[4]arene: Searching for the Missing Fifth Conformer

Popis výsledku v původním jazyce

Contrary to theoretical predictions, direct alkylation of 2,14-dithiacalix[4]arene provides only four out of five basic conformers (atropisomers). To prepare the missing 1,2 (C)-alternate conformer, the indirect alkylation strategy was applied using 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane as a protective agent. As proved by the combination of NMR and X-ray crystallography, the position of the disiloxane bridge on the macrocycle is not fixed and can be changed under basic conditions, representing thus so far unknown rearrangement of the siloxane moiety. The subsequent dialkylation/deprotection and dialkylation enabled the synthesis of the last missing conformer. As demonstrated by several examples, the mixed-bridge macrocycle (with both CH2 and S bridging units) enables preparation of unusual conformers or substitution patterns, which are difficult to obtain, if at all, in classical calixarene chemistry. This feature makes 2,14-dithiacalix[4]arene a very promising candidate for the role of molecular scaffold or platform in various supramolecular applications.

Název v anglickém jazyce

Chemistry of 2,14-Dithiacalix[4]arene: Searching for the Missing Fifth Conformer

Popis výsledku anglicky

Contrary to theoretical predictions, direct alkylation of 2,14-dithiacalix[4]arene provides only four out of five basic conformers (atropisomers). To prepare the missing 1,2 (C)-alternate conformer, the indirect alkylation strategy was applied using 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane as a protective agent. As proved by the combination of NMR and X-ray crystallography, the position of the disiloxane bridge on the macrocycle is not fixed and can be changed under basic conditions, representing thus so far unknown rearrangement of the siloxane moiety. The subsequent dialkylation/deprotection and dialkylation enabled the synthesis of the last missing conformer. As demonstrated by several examples, the mixed-bridge macrocycle (with both CH2 and S bridging units) enables preparation of unusual conformers or substitution patterns, which are difficult to obtain, if at all, in classical calixarene chemistry. This feature makes 2,14-dithiacalix[4]arene a very promising candidate for the role of molecular scaffold or platform in various supramolecular applications.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2021

Kód důvěrnosti údajů

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

Název periodika

Journal of Organic Chemistry

ISSN

0022-3263

e-ISSN

—

Svazek periodika

86

Číslo periodika v rámci svazku

14

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

14

Strana od-do

9788-9801

Kód UT WoS článku

000674931400045

EID výsledku v databázi Scopus

2-s2.0-85110982651