Enantioselective Synthesis of C−O Axially Chiral Diaryl Ethers by NHC‐Catalyzed Atroposelective Desymmetrization**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(52)

Опубликована: Ноя. 21, 2023

Axially chiral diaryl ethers, a distinguished class of atropisomers possessing unique dual C-O axis, hold immense potential for diverse research domains. In contrast to the catalytic enantioselective synthesis conventional single axis bearing atropisomers, atroposelective axially ethers containing flexible remains significant challenge. Herein, we demonstrate first N-heterocyclic carbene (NHC)-catalyzed via esterification dialdehyde-containing ethers. Mechanistically, reaction proceeds NHC-catalyzed desymmetrization strategy afford corresponding ether in good yields and high enantioselectivities under mild conditions. The derivatization synthesized product expands utility present access library compounds. temperature dependency preliminary investigations on racemization barrier bonds are also presented.

Язык: Английский

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Oxidative N‐Heterocyclic Carbene Catalysis

Chemistry - A European Journal, Год журнала: 2022, Номер 29(4)

Опубликована: Окт. 7, 2022

N-Heterocyclic carbene (NHC) catalysis is a by now consolidated organocatalytic platform for number of synthetic (asymmetric) transformations via diverse reaction modes/intermediates. In addition to the typical umpolung processes involving acyl anion/homoenolate equivalent species, implementation protocols under oxidative conditions greatly expands possibilities this methodology. Oxidative NHC-catalysis allows and oxygenative through specific manipulations Breslow-type species depending upon oxidant used (external or O

Язык: Английский

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N-Heterocyclic carbene-catalyzed enantioselective (dynamic) kinetic resolutions and desymmetrizations

Science China Chemistry, Год журнала: 2023, Номер 67(2), С. 482 - 511

Опубликована: Сен. 11, 2023

Язык: Английский

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N-Heterocyclic Carbene-Catalyzed Atroposelective Synthesis of N–N Axially Chiral 3-Amino Quinazolinones

ACS Catalysis, Год журнала: 2023, Номер 13(13), С. 8752 - 8759

Опубликована: Июнь 16, 2023

Although the atroposelective synthesis of biaryls and related compounds bearing axially chiral C–C bonds is well-known, C–N bond-containing relatively less explored, construction N–N has received only scant attention. Demonstrated herein N-heterocyclic carbene (NHC)-catalyzed selective amidation reaction, leading to 3-amino quinazolinones. The NHC-catalyzed reaction quinazolinones containing a free N–H moiety with α,β-unsaturated aldehydes under oxidative conditions furnished atropisomeric quinazolinone derivatives mild broad scope. Preliminary studies on experimental density functional theory-based rotational barrier determination are also presented.

Язык: Английский

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Elucidating the mechanism and origin of stereoselectivity in the activation/transformation of an acetic ester catalyzed by an N-heterocyclic carbene

Physical Chemistry Chemical Physics, Год журнала: 2024, Номер 26(5), С. 4320 - 4328

Опубликована: Янв. 1, 2024

The detailed mechanism, origin of stereoselectivity and substrate catalyst effects are extensively investigated using DFT methods.

Язык: Английский

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Asymmetric synthesis of spirofuro[2,3-b]azepine-5,3′-indoline derivativesviacycloisomerization/[4 + 3] annulation process under Au/N-heterocyclic carbene relay catalysis

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(13), С. 3347 - 3352

Опубликована: Янв. 1, 2023

A variety of enantioenriched spirofuro[2,3- b ]azepine-5,3’-indoline derivatives were synthesized via Au(I)/chiral NHC relay catalyzed cycloisomerization/asymmetric [4+3] annulation.

Язык: Английский

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Dark and Light Reactions of Carbenes─Merging Carbene Transfer Reactions with N-Heterocyclic Carbene Catalysis for the Synthesis of Hydroxamic Acid Esters

ACS Catalysis, Год журнала: 2022, Номер 12(18), С. 11129 - 11136

Опубликована: Авг. 30, 2022

Herein, we report visible light and N-heterocyclic carbene (NHC) jointly promoted multicomponent transfer reactions. Under the optimized reaction conditions, two kinds of important hydroxamic acid esters were obtained in good yields depending on media used. The key to this success was driven by blue light-promoted generation free species fast situ formation under NHC-catalyzed conditions. mild excellent functional group tolerance, useful synthetic transformations, successful modification natural products drug molecules proved utility practicality method.

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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Mechanism and Origin of Stereoselectivity of N-Heterocyclic Carbene (NHC)-Catalyzed Transformation Reaction of Benzaldehyde with o-QDM as Key Intermediate: A DFT Study

The Journal of Physical Chemistry A, Год журнала: 2024, Номер 128(30), С. 6190 - 6198

Опубликована: Июль 18, 2024

N-heterocyclic carbene (NHC)-bound

Язык: Английский

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NHC-Catalyzed Enantioselective Synthesis of Tetracyclic δ-Lactones by (4 + 2) Annulation of ortho-Quinodimethanes with Activated Ketones

Organic Letters, Год журнала: 2023, Номер 25(43), С. 7852 - 7857

Опубликована: Окт. 20, 2023

The N-heterocyclic carbene (NHC)-catalyzed generation of ortho-quinodimethanes (o-QDMs) from 9H-fluorene-1-carbaldehydes followed by the interception with activated ketones resulting in enantioselective synthesis tetracyclic δ-lactones is presented. High diastereoselectivity products, remote C(sp3)-H functionalization, broad substrate scope, and mild reaction conditions are notable features present (4 + 2) annulation.

Язык: Английский

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