Torsional Strain‐Independent Catalytic Enantioselective Synthesis of Biaryl Atropisomers

Angewandte Chemie, Год журнала: 2022, Номер 134(43)

Опубликована: Авг. 26, 2022

Abstract Catalytic asymmetric dynamic kinetic resolution of configurationally labile bridged biaryls is emerging as a powerful strategy for atropisomer synthesis. However, the reported examples suffer from an inherent challenge reactivity highly dependent on torsional strain biaryl substrates, which significantly narrows down scope and hampers application. Herein, we report our discovery development strain‐independent reaction between thionolactones activated isocyanides. By employing auto‐tandem silver catalysis, universal synthesis both tri ‐ tetra ortho ‐substituted thiazole‐containing was realized in high yields with enantioselectivities. In addition, these products could be facilely converted to novel type bearing eight‐membered lactone. Mechanistic studies were carried out elucidate cause this unusual reactivity.

Язык: Английский

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Organocatalytic Enantioselective Synthesis of Axially ChiralN,N′‐Bisindoles

Angewandte Chemie, Год журнала: 2023, Номер 135(15)

Опубликована: Фев. 7, 2023

Abstract This study establishes the first organocatalytic enantioselective synthesis of axially chiral N , N′ ‐bisindoles via phosphoric acid‐catalyzed formal (3+2) cycloadditions indole‐based enaminones as novel platform molecules with 2,3‐diketoesters, where de novo indole‐ring formation is involved. Using this new strategy, various were synthesized in good yields and excellent enantioselectivities (up to 87 % yield 96 ee). More importantly, class exhibited some degree cytotoxicity toward cancer cells was derived into phosphine ligands high catalytic activity. provides a strategy for using asymmetric organocatalysis realize applications such scaffolds medicinal chemistry catalysis.

Язык: Английский

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Atroposelective Access to 1,3‐Oxazepine‐Containing Bridged Biaryls via Carbene‐Catalyzed Desymmetrization of Imines

Angewandte Chemie, Год журнала: 2022, Номер 135(1)

Опубликована: Сен. 10, 2022

Abstract We disclose herein an atroposelective synthesis of novel bridged biaryls containing medium‐sized rings via N‐heterocyclic carbene organocatalysis. The reaction starts with addition the catalyst to aminophenol‐derived aldimine substrate. Subsequent oxidation and intramolecular desymmetrization lead formation 1,3‐oxazepine‐containing in good yields excellent enantioselectivities. These biaryl products can be readily transformed into chiral phosphite ligands. Preliminary density function theory calculations suggest that origin enantioselectivity arises from more favorable frontier molecular orbital interactions transition state leading major product.

Язык: Английский

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