Enhanced single-isomer separation and pseudoenantiomer resolution of new primary rim heterobifunctionalized alpha-cyclodextrin derivatives

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F18%3A10389370" target="_blank" >RIV/00216208:11310/18:10389370 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.3762/bjoc.14.261" target="_blank" >https://doi.org/10.3762/bjoc.14.261</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.3762/bjoc.14.261" target="_blank" >10.3762/bjoc.14.261</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Enhanced single-isomer separation and pseudoenantiomer resolution of new primary rim heterobifunctionalized alpha-cyclodextrin derivatives

Popis výsledku v původním jazyce

The synthesis of batch-to-batch reproducible cyclodextrin (CD) derivatives often requires functionalization at specific positions of the CD skeleton. However, the regioselective preparation of this type of CD derivatives remains a challenge in synthetic chemistry. Thus, the present study aimed to prepare all positional regioisomers on the primary rim of homobifunctionalized diazido-alpha-CDs by selective substitution on the primary rim. Specifically, three positional regioisomers 6(A),6(B)-6(A),6(C), and 6(A),6(D) diazido-alpha-CDs were prepared via different intermediates (using sulfonylation with capping agents, bromination and tosylation). Furthermore, heterobifunctionalized 6(A)-azido-6(x)-mesitylenesulfonyl-alpha-CDs were also synthesized, and all regioisomers were successfully separated by HPLC. Moreover, the heterobifunctionalized alpha-CD regioisomers were isolated in gram-scale quantities, isomers AB and AC in the form of a pseudoenantiomeric mixture. The pseudoenantiomers AC/CA and AB/BA were resolved on an analytical scale by HPLC-MS at 10 degrees C. Thus, the presented synthetic and analytical methods for homo- and heterodisubstituted alpha-CDs are efficient and reproducible for the preparation of various pure regioisomeric CD derivatives. Accordingly, our findings indicate, (i) the versatility of selectively modified azido and mesitylene CD skeletons in preparing new types of alpha-CD derivatives and (ii) the potential of using resolved alpha-CD pseudoenantiomers in other research fields such as organocatalysis.

Název v anglickém jazyce

Enhanced single-isomer separation and pseudoenantiomer resolution of new primary rim heterobifunctionalized alpha-cyclodextrin derivatives

Popis výsledku anglicky

The synthesis of batch-to-batch reproducible cyclodextrin (CD) derivatives often requires functionalization at specific positions of the CD skeleton. However, the regioselective preparation of this type of CD derivatives remains a challenge in synthetic chemistry. Thus, the present study aimed to prepare all positional regioisomers on the primary rim of homobifunctionalized diazido-alpha-CDs by selective substitution on the primary rim. Specifically, three positional regioisomers 6(A),6(B)-6(A),6(C), and 6(A),6(D) diazido-alpha-CDs were prepared via different intermediates (using sulfonylation with capping agents, bromination and tosylation). Furthermore, heterobifunctionalized 6(A)-azido-6(x)-mesitylenesulfonyl-alpha-CDs were also synthesized, and all regioisomers were successfully separated by HPLC. Moreover, the heterobifunctionalized alpha-CD regioisomers were isolated in gram-scale quantities, isomers AB and AC in the form of a pseudoenantiomeric mixture. The pseudoenantiomers AC/CA and AB/BA were resolved on an analytical scale by HPLC-MS at 10 degrees C. Thus, the presented synthetic and analytical methods for homo- and heterodisubstituted alpha-CDs are efficient and reproducible for the preparation of various pure regioisomeric CD derivatives. Accordingly, our findings indicate, (i) the versatility of selectively modified azido and mesitylene CD skeletons in preparing new types of alpha-CD derivatives and (ii) the potential of using resolved alpha-CD pseudoenantiomers in other research fields such as organocatalysis.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

—

Návaznosti

S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Beilstein Journal of Organic Chemistry

ISSN

1860-5397

e-ISSN

—

Svazek periodika

14

Číslo periodika v rámci svazku

November

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

2829-2837

Kód UT WoS článku

000451065200001

EID výsledku v databázi Scopus

2-s2.0-85056986656