Primary and Secondary Amines by Flavin-Photocatalyzed Consecutive Desulfonylation and Dealkylation of Sulfonamides

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F23%3A00579795" target="_blank" >RIV/61388963:_____/23:00579795 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60461373:22310/23:43928497

Výsledek na webu

<a href="https://doi.org/10.1002/adsc.202300843" target="_blank" >https://doi.org/10.1002/adsc.202300843</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/adsc.202300843" target="_blank" >10.1002/adsc.202300843</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Primary and Secondary Amines by Flavin-Photocatalyzed Consecutive Desulfonylation and Dealkylation of Sulfonamides

Popis výsledku v původním jazyce

Alkane-, arene-, and perfluoroalkanesulfonyl groups are widely used in organic synthesis to protect amino functionalities or to facilitate their installation. Protection of amino functions by a sulfonyl group to form sulfonamides is advantageous as they are easy to purify and tolerate various reaction conditions. On the other hand, sulfonyl group removal is difficult. Herein, we present a versatile metal-free photocatalytic reductive method for desulfonylation of sulfonamides and aryl sulfonates to the parent amines mediated by flavin derivatives, namely deazaisoalloxazines and deazaalloxazines, and visible light. Photocatalysis with 5-deazalloxazines is shown to even mediate the cleavage of perfluoroalkanesulfonamides (triflylamides and nonaflylamides), which is significantly more difficult than that of other sulfonamides and has previously not been achieved by photochemical means. The method is shown to perform consecutive desulfonylation and dealkylation of N-alkyl-N-phenylperfluoroalkanesulfonamides affording primary anilines. This occurs via consecutive reductive and oxidative catalytic cycles mediated by the flavin catalyst. The perfluoroalkylsulfonyl group fulfils a dual role serving as a protecting group and, after removal by the reductive cycle, as the species driving the oxidative dealkylation reaction.

Název v anglickém jazyce

Primary and Secondary Amines by Flavin-Photocatalyzed Consecutive Desulfonylation and Dealkylation of Sulfonamides

Popis výsledku anglicky

Alkane-, arene-, and perfluoroalkanesulfonyl groups are widely used in organic synthesis to protect amino functionalities or to facilitate their installation. Protection of amino functions by a sulfonyl group to form sulfonamides is advantageous as they are easy to purify and tolerate various reaction conditions. On the other hand, sulfonyl group removal is difficult. Herein, we present a versatile metal-free photocatalytic reductive method for desulfonylation of sulfonamides and aryl sulfonates to the parent amines mediated by flavin derivatives, namely deazaisoalloxazines and deazaalloxazines, and visible light. Photocatalysis with 5-deazalloxazines is shown to even mediate the cleavage of perfluoroalkanesulfonamides (triflylamides and nonaflylamides), which is significantly more difficult than that of other sulfonamides and has previously not been achieved by photochemical means. The method is shown to perform consecutive desulfonylation and dealkylation of N-alkyl-N-phenylperfluoroalkanesulfonamides affording primary anilines. This occurs via consecutive reductive and oxidative catalytic cycles mediated by the flavin catalyst. The perfluoroalkylsulfonyl group fulfils a dual role serving as a protecting group and, after removal by the reductive cycle, as the species driving the oxidative dealkylation reaction.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GF21-14200K" target="_blank" >GF21-14200K: Cílený návrh flavinů pro organickou fotokatalýzu</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Advanced Synthesis & Catalysis

ISSN

1615-4150

e-ISSN

1615-4169

Svazek periodika

365

Číslo periodika v rámci svazku

24

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

10

Strana od-do

4662-4671

Kód UT WoS článku

001102447100001

EID výsledku v databázi Scopus

2-s2.0-85177467751