Controlling Stereoselectivity with Noncovalent Interactions in Chiral Phosphoric Acid Organocatalysis

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Март 18, 2025

Chiral phosphoric acids (CPAs) have emerged as highly effective Brønsted acid catalysts in an expanding range of asymmetric transformations, often through novel multifunctional substrate activation modes. Versatile and broadly appealing, these benefit from modular tunable structures, compatibility with additives. Given the unique types noncovalent interactions (NCIs) that can be established between CPAs various reactants─such hydrogen bonding, aromatic interactions, van der Waals forces─it is unsurprising catalyst systems become a promising approach for accessing diverse chiral product outcomes. This review aims to provide in-depth exploration mechanisms by which impart stereoselectivity, positioning NCIs central feature connects broad spectrum catalytic reactions. Spanning literature 2004 2024, it covers nucleophilic additions, radical atroposelective bond formations, highlighting applicability CPA organocatalysis. Special emphasis placed on structural mechanistic features govern CPA-substrate well tools techniques developed enhance our understanding their behavior. In addition emphasizing details stereocontrolling elements individual reactions, we carefully structured this natural progression specifics broader, class-level perspective. Overall, findings underscore critical role catalysis significant contributions advancing synthesis.

Язык: Английский

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Enantioselective Aminative Dearomatization of Indoles via Electrophilic 1,6-Addition of p-Quinone Diimides (p-QDIs)

Organic Letters, Год журнала: 2024, Номер 26(23), С. 4932 - 4937

Опубликована: Июнь 3, 2024

Herein we report the first use of p-quinone diimide for aminative dearomatization 2,3-disubstituted indoles to furnish C3 aza-quaternary chiral indolenines. This approach, which proceeds via an electrophilic 1,6-addition diimide, allows synthesis array optically active indolenines with high yields and excellent enantioselectivities. A one-pot approach same has also been established further improve synthetic accessibility this protocol.

Язык: Английский

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NCI-driven regioselectivity and enantioreversal in chiral phosphoric acid-catalyzed arylamine functionalization

Organic Chemistry Frontiers, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Non-covalent interactions (NCIs) have emerged as pivotal elements in asymmetric catalysis, enabling precise control over reactivity and selectivity complex transformations.

Язык: Английский

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B(C6F5)3/CPA‐Catalyzed Aza‐Diels–Alder Reaction of 3,3‐Difluoro‐2‐Aryl‐3H‐indoles and Unactivated Dienes

Chemistry - A European Journal, Год журнала: 2024, Номер 30(34)

Опубликована: Апрель 16, 2024

Abstract Here we report B(C 6 F 5 ) 3/ CPA‐catalyzed enantioselective aza‐Diels–Alder reaction of 3,3‐difluoro‐2‐Aryl‐3 H ‐indoles with unactivated dienes to access chiral 10,10‐difluoro‐tetrahydropyrido[1,2‐ a ]indoles. This protocol allows the formation pyrazole‐based C2‐quaternary indolin‐3‐ones high enantioselectivities and regioselectivities. Moreover, gram‐scale synthesis ]indole skeleton was successfully achieved without any reduction in both yield enantioselectivity.

Язык: Английский

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Synthesis of Fluorine‐containing C2‐Tetrasubstituted Indolin‐3‐ones via Rapid Incorporation of Difluoroacetate Radical into 2‐Aryl‐3H‐indol‐3‐ones

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(31)

Опубликована: Июнь 7, 2024

Abstract Here, we have successfully achieved the addition of difluoroacetate radicals to 2‐aryl‐3 H ‐indol‐3‐ones, enabling various difluoroalkylations C2‐tetrasubstituted 2‐aryl indolin‐3‐ones in a highly efficient and economical manner. It is worth mentioning that these difluoroalkylation compounds can be easily transformed into derivatives under mild reaction conditions. Control experiments suggest involvement ethyl radical species reaction.

Язык: Английский

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