Tin-catalyzed reductive coupling of amines with CO2 and H2

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F23%3A10457933" target="_blank" >RIV/00216208:11310/23:10457933 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=MspUi01HNG" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=MspUi01HNG</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d2cy01659a" target="_blank" >10.1039/d2cy01659a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Tin-catalyzed reductive coupling of amines with CO2 and H2

Popis výsledku v původním jazyce

Reductive coupling of amines with CO2 and H2 can be catalyzed by transition metals. However, functional group (FG) tolerance is improved when using auxiliary main group hydrides (instead of H2), which makes them more suitable for the synthesis of functionalized molecules. Replacing auxiliary main group hydrides with frustrated Lewis pairs (FLPs) can, in theory, generate comparably selective hydrides in situ from H2 activation. Herein, we report the selective N-formylation of amines via CO2 hydrogenation catalyzed by a series of R3SnX (R = alkyl, X = Cl, OTf, NTf2, ClO4) Lewis acids, which form an FLP with the amine substrate and/or 2,4,6-collidine. FLP dihydrogen activation leads to the in situ formation of an R3Sn-H species with excellent selectivity toward CO2 hydrogenation over other reducible FGs. Consequently, amines containing alkenes, amides, esters, and carboxylic acids can be N-formylated with CO2 and H2. Increasing the steric bulk of the alkyl substituents prevents the redistribution of the R3SnX Lewis acid to R4Sn and R2SnX2, which is the primary cause of catalyst decomposition. Cy3SnOTf reached turnovers of &gt;300 and amine conversions of up to 100%. In addition to synthesis, isolation, and testing of key intermediates for their reactivity, we identified an off-cycle intermediate by in operando (1)H NMR spectroscopy and therefore propose a mechanistic cycle. By avoiding the use of any transition metals or auxiliary main group hydrides, our procedure opens a pathway for developing transition-metal-free CO2 hydrogenation methods utilising hydrogen gas.

Název v anglickém jazyce

Tin-catalyzed reductive coupling of amines with CO2 and H2

Popis výsledku anglicky

Reductive coupling of amines with CO2 and H2 can be catalyzed by transition metals. However, functional group (FG) tolerance is improved when using auxiliary main group hydrides (instead of H2), which makes them more suitable for the synthesis of functionalized molecules. Replacing auxiliary main group hydrides with frustrated Lewis pairs (FLPs) can, in theory, generate comparably selective hydrides in situ from H2 activation. Herein, we report the selective N-formylation of amines via CO2 hydrogenation catalyzed by a series of R3SnX (R = alkyl, X = Cl, OTf, NTf2, ClO4) Lewis acids, which form an FLP with the amine substrate and/or 2,4,6-collidine. FLP dihydrogen activation leads to the in situ formation of an R3Sn-H species with excellent selectivity toward CO2 hydrogenation over other reducible FGs. Consequently, amines containing alkenes, amides, esters, and carboxylic acids can be N-formylated with CO2 and H2. Increasing the steric bulk of the alkyl substituents prevents the redistribution of the R3SnX Lewis acid to R4Sn and R2SnX2, which is the primary cause of catalyst decomposition. Cy3SnOTf reached turnovers of &gt;300 and amine conversions of up to 100%. In addition to synthesis, isolation, and testing of key intermediates for their reactivity, we identified an off-cycle intermediate by in operando (1)H NMR spectroscopy and therefore propose a mechanistic cycle. By avoiding the use of any transition metals or auxiliary main group hydrides, our procedure opens a pathway for developing transition-metal-free CO2 hydrogenation methods utilising hydrogen gas.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GM21-27431M" target="_blank" >GM21-27431M: Lewisovy kyseliny a frustrované Lewisovy páry pro redukčně kondenzační reakce oxidu uhličitého s aminy</a><br>

Návaznosti

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

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Catalysis: Science and Technology

ISSN

2044-4753

e-ISSN

2044-4761

Svazek periodika

13

Číslo periodika v rámci svazku

3

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

8

Strana od-do

637-644

Kód UT WoS článku

000896820400001

EID výsledku v databázi Scopus

2-s2.0-85144746739