Desymmetric esterification catalysed by bifunctional chiral N-heterocyclic carbenes provides access to inherently chiral calix[4]arenes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F25%3A10498969" target="_blank" >RIV/00216208:11310/25:10498969 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=poYQcu768-" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=poYQcu768-</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1038/s41467-025-59781-4" target="_blank" >10.1038/s41467-025-59781-4</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Desymmetric esterification catalysed by bifunctional chiral N-heterocyclic carbenes provides access to inherently chiral calix[4]arenes

Popis výsledku v původním jazyce

Calix[4]arenes display inherent chirality, with broad applications in synthetic and medicinal chemistry and in materials sciences. However, their use is hindered by their limited synthetic accessibility, primarily due to the lack of enantioselective methods for preparing chiral calix[4]arenes with an ABCC substitution pattern. Here, we address this challenge by presenting a simple, efficient, and metal-free protocol for organocatalytic desymmetrisation of prochiral diformylcalix[4]arenes. Through this highly effective and sustainable approach, we synthesize structurally unique products in gram-scale reactions. Accordingly, this method facilitates extensive post-functionalisations of the carbonyl groups, including for organocatalyst development. Furthermore, our experimental mechanistic studies demonstrate that desymmetrisation determines enantiocontrol in esterification reactions catalysed by N-heterocyclic carbenes. These findings underscore the broad potential of this method for providing versatile access to inherently chiral calix[4]arenes with an ABCC substitution pattern while offering a valuable platform for asymmetric molecular recognition and catalysis.

Název v anglickém jazyce

Desymmetric esterification catalysed by bifunctional chiral N-heterocyclic carbenes provides access to inherently chiral calix[4]arenes

Popis výsledku anglicky

Calix[4]arenes display inherent chirality, with broad applications in synthetic and medicinal chemistry and in materials sciences. However, their use is hindered by their limited synthetic accessibility, primarily due to the lack of enantioselective methods for preparing chiral calix[4]arenes with an ABCC substitution pattern. Here, we address this challenge by presenting a simple, efficient, and metal-free protocol for organocatalytic desymmetrisation of prochiral diformylcalix[4]arenes. Through this highly effective and sustainable approach, we synthesize structurally unique products in gram-scale reactions. Accordingly, this method facilitates extensive post-functionalisations of the carbonyl groups, including for organocatalyst development. Furthermore, our experimental mechanistic studies demonstrate that desymmetrisation determines enantiocontrol in esterification reactions catalysed by N-heterocyclic carbenes. These findings underscore the broad potential of this method for providing versatile access to inherently chiral calix[4]arenes with an ABCC substitution pattern while offering a valuable platform for asymmetric molecular recognition and catalysis.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GA24-12575S" target="_blank" >GA24-12575S: Přenos chirality pomocí organokatalýzy</a><br>

Návaznosti

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

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

Nature Communications

ISSN

2041-1723

e-ISSN

2041-1723

Svazek periodika

16

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

4443

Kód UT WoS článku

001492295900008

EID výsledku v databázi Scopus

2-s2.0-105004896080