Trivalent Metal Lewis Acids Activate CO2 in Transfer Hydrogenations

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F25%3A10503575" target="_blank" >RIV/00216208:11310/25:10503575 - isvavai.cz</a>

Výsledek na webu

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

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cssc.202500629" target="_blank" >10.1002/cssc.202500629</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Trivalent Metal Lewis Acids Activate CO2 in Transfer Hydrogenations

Popis výsledku v původním jazyce

Using γ-terpinene as a bio-derived H-2 surrogate, trivalent metal MX(3) (M = Al, Ga, In, Yb, X = Cl, OTf) Lewis acids (LAs) catalyze CO2 hydrogenation to formate, yielding p-cymene as the by-product. The resulting formate produces up to 91% N-formamides in tandem hydrogenation-coupling reactions and up to 95% heterocycles, including azoles, via further in situ transfer formylation to ortho-substituted anilines and cyclization at 130 °C and 4 bar. But In(OTf)(3) and a Lewis base fail to abstract a hydride from γ-terpinene. Unlike other LAs and transfer hydrogenation catalysts that induce hydride abstraction from 1,4-cyclohexadiene(s) over B(C6F5)(3), alkali earth or noble metals, MX3 LAs activate CO2, so CO2 can directly accept a hydride from γ-terpinene during formate synthesis, as shown by density functional theory calculations. This triple role of MX3 LAs in promoting (1) CO2 activation, (2) tandem coupling reactions, and (3) transfer formylation at low pressure paves the way for sustainable CO2 hydrogenation processes, leveraging bio-derived H2 surrogates to develop efficient carbon capture and utilization systems and to synthesize valuable compounds from renewable feedstocks.

Název v anglickém jazyce

Trivalent Metal Lewis Acids Activate CO2 in Transfer Hydrogenations

Popis výsledku anglicky

Using γ-terpinene as a bio-derived H-2 surrogate, trivalent metal MX(3) (M = Al, Ga, In, Yb, X = Cl, OTf) Lewis acids (LAs) catalyze CO2 hydrogenation to formate, yielding p-cymene as the by-product. The resulting formate produces up to 91% N-formamides in tandem hydrogenation-coupling reactions and up to 95% heterocycles, including azoles, via further in situ transfer formylation to ortho-substituted anilines and cyclization at 130 °C and 4 bar. But In(OTf)(3) and a Lewis base fail to abstract a hydride from γ-terpinene. Unlike other LAs and transfer hydrogenation catalysts that induce hydride abstraction from 1,4-cyclohexadiene(s) over B(C6F5)(3), alkali earth or noble metals, MX3 LAs activate CO2, so CO2 can directly accept a hydride from γ-terpinene during formate synthesis, as shown by density functional theory calculations. This triple role of MX3 LAs in promoting (1) CO2 activation, (2) tandem coupling reactions, and (3) transfer formylation at low pressure paves the way for sustainable CO2 hydrogenation processes, leveraging bio-derived H2 surrogates to develop efficient carbon capture and utilization systems and to synthesize valuable compounds from renewable feedstocks.

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

2025

Kód důvěrnosti údajů

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

Název periodika

ChemSusChem

ISSN

1864-5631

e-ISSN

1864-564X

Svazek periodika

18

Číslo periodika v rámci svazku

16

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

5

Strana od-do

e202500629

Kód UT WoS článku

001524861000001

EID výsledku v databázi Scopus

2-s2.0-105010055651