Tale of the Breslow intermediate, a central player in N-heterocyclic carbene organocatalysis: then and now

Chemical Science, Год журнала: 2021, Номер 12(23), С. 7973 - 7992

Опубликована: Янв. 1, 2021

Molecular insights on the formation, detection, and even isolation of Breslow intermediate, which is most important species in N-heterocyclic carbene (NHC) catalysis, as obtained from experimental computational studies, are presented.

Язык: Английский

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Electrochemically promoted N-heterocyclic carbene polymer-catalyzed cycloaddition of aldehyde with isocyanide acetate

Science China Chemistry, Год журнала: 2022, Номер 65(10), С. 1873 - 1878

Опубликована: Сен. 15, 2022

Язык: Английский

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Exploring a general mechanistic map on NHC-catalyzed activation/transformation reactions of saturated carboxylic anhydrides

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(11), С. 2670 - 2679

Опубликована: Янв. 1, 2023

A general mechanistic map involving multiple intermediates and pathways has been proposed systematically studied for NHC-catalyzed transformation reactions of saturated carboxylic anhydrides.

Язык: Английский

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Carbene-Catalyzed Enantioselective Sulfonylation of Enone Aryl Aldehydes: A New Mode of Breslow Intermediate Oxidation

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(12), С. 5441 - 5449

Опубликована: Март 11, 2022

A carbene-catalyzed sulfonylation reaction between enone aryl aldehydes and sulfonyl chlorides is disclosed. The effectively installs sulfone moieties in a highly enantioselective manner to afford sulfone-containing bicyclic lactones. chloride behaves both as an oxidant nucleophilic substrate (via its reduced form) this N-heterocyclic carbene (NHC)-catalyzed process. NHC catalyst provides activation stereoselectivity control on very remote site of aldehyde substrates. Water plays important role modulating deactivation reactivation routes that involve reactions chloride. Experimental studies DFT calculations suggest unprecedented intermediate new oxidation mode the NHC-derived Breslow are involved asymmetric reaction.

Язык: Английский

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N-Heterocyclic Carbene/Brønsted Acid Cooperatively Catalyzed Conversions of α, β-Unsaturated Carbonyls: Hydrogen Bond Donor/Acceptor-Electrophile/Nucleophile Combination Models

ACS Catalysis, Год журнала: 2022, Номер 13(1), С. 612 - 623

Опубликована: Дек. 22, 2022

Great success has been achieved in precisely constructing C–C bonds under N-heterocyclic carbene (NHC)/Brønsted acid (BA) cooperative catalysis. However, how NHC and BA co-catalyst accelerate conversions of α,β-unsaturated carbonyls remains unclear. Herein, we have systematically studied several representative NHC/BA catalysis models to help chemists better understand the nature these reactions. The favorable cooperatively catalyzed reactions were identified confirmed by proposed hydrogen bond donor/acceptor-electrophile/nucleophile combination rules reactivity index (denoted as Rk). This work should be important for understanding catalytic mechanism also provides valuable insights designing an efficient reaction with special selectivity.

Язык: Английский

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Unraveling the mechanism and substituent effects on the N-heterocyclic carbene-catalyzed transformation reaction of enals and imines

Molecular Catalysis, Год журнала: 2022, Номер 519, С. 112122 - 112122

Опубликована: Янв. 14, 2022

Язык: Английский

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Mechanism of a cobalt-catalyzed hydroarylation reaction and origin of stereoselectivity

Catalysis Science & Technology, Год журнала: 2022, Номер 12(13), С. 4380 - 4387

Опубликована: Янв. 1, 2022

In the present study, mechanism of a cobalt-catalyzed hydroarylation reaction between N -pyridylindole and 1,6-enynes origin its stereoselectivity have been systematically investigated using DFT calculation method.

Язык: Английский

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Deaminative radical reactions via relayed proton-coupled electron transfer

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(9), С. 2155 - 2164

Опубликована: Янв. 1, 2023

The detailed mechanism of these kinds N-heterocyclic carbene-catalyzed deaminative radical reactions has been explored in theory for the first time.

Язык: Английский

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Disclosing the mechanism and origin of stereoselectivity of the NHC-catalyzed transformation reaction of enals with acyl azolium as a key intermediate

Catalysis Science & Technology, Год журнала: 2024, Номер 14(15), С. 4302 - 4310

Опубликована: Янв. 1, 2024

The reaction mechanism and origin of stereoselectivity the NHC-catalyzed transformation an acyl azolium intermediate have been theoretically investigated using DFT method.

Язык: Английский

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Theoretical study of the NHC-catalyzed C–S bond cleavage and reconstruction reaction: mechanism, stereoselectivity, and role of catalysts

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(19), С. 5352 - 5360

Опубликована: Янв. 1, 2021

The mechanism of the NHC-catalyzed C–S bond activation reaction has been theoretically studied and ELF analysis along with IRC results shows that NHC promotes cleavage via an S N 2 process.

Язык: Английский

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