Organocatalytic Enantioselective Synthesis of Axially ChiralN,N′‐Bisindoles

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Фев. 7, 2023

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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Atropisomers with Axial and Point Chirality: Synthesis and Applications

Accounts of Chemical Research, Год журнала: 2022, Номер 55(18), С. 2545 - 2561

Опубликована: Сен. 9, 2022

ConspectusEnantiopure atropisomers have become increasingly important in asymmetric synthesis and catalysis, pharmaceutical science, material science since the discovery of inherent features axial chirality originating from rotational restriction. Despite advances made this field to date, it remains highly desirable construct structurally diverse with potentially useful functions. We propose superposition match point as a strategy access complex building blocks for organic because merging atropisomeric backbones one or more extra chiral elements can topologically broaden three-dimensional environments create scaffolds multiple tunable parameters. Over past decade, we successfully implemented strategic design develop series enantiopure utilized synergistic functions these molecules enhance transfer various catalytic transformations.In Account, present several novel superposed developed our laboratory. In studies, was used synthesize both biaryl non-biaryl commercially available sources. Consequently, were demonstrate importance synergetic specific enantioselective reactions. For example, aromatic amide-derived atropisomers, simplified Xing-Phos arrays, broadly employed Ag-catalyzed [3 + 2] cycloaddition by reactions aldiminoesters activated alkenes imines, well being solvating agents discrimination optically active mandelic acid derivatives. Considering powerful potential also explored transition-metal-catalyzed construction backbone (Ar–alkene, Ar–N axis) bearing ligands functional molecules.The studies presented herein are expected stimulate further research efforts on development matching chirality. addition electron stereohindrance effects, synergy between axial/point groups is proven be special function that cannot ignored promoting reactivity chirality-transfer efficiency synthesis. types capable versatile coordination metal catalysts catalysis highlight power synthetically atropisomers.

Язык: Английский

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Synthesis of Axially ChiralN‐Arylindoles via Atroposelective Cyclization of Ynamides Catalyzed by Chiral Brønsted Acids

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(20)

Опубликована: Март 5, 2022

In recent years, asymmetric catalysis of ynamides has attracted much attention, but these reactions mostly constructed central chirality, except for a few examples on the synthesis axially chiral compounds which exclusively relied noble-metal catalysis. Herein, facile access to N-heterocycles enabled by Brønsted acid-catalyzed 5-endo-dig cyclization is disclosed, represents first metal-free protocol construction from ynamides. This method allows practical and atom-economical valuable N-arylindoles in excellent yields with generally enantioselectivities. Moreover, organocatalysts ligands based such N-arylindole skeletons are demonstrated be applicable

Язык: Английский

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Progress in organocatalytic asymmetric (4+3) cycloadditions for the enantioselective construction of seven-membered rings

Science China Chemistry, Год журнала: 2023, Номер 66(4), С. 966 - 992

Опубликована: Фев. 15, 2023

Язык: Английский

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The Catalytic Formation of Atropisomers and Stereocenters via Asymmetric Suzuki–Miyaura Couplings

ACS Catalysis, Год журнала: 2022, Номер 12(9), С. 4918 - 4937

Опубликована: Апрель 12, 2022

Although Suzuki–Miyaura cross-coupling is one of the most convenient and well-developed reactions, its applications to asymmetric version deliver highly functionalized atropisomers or nonracemic coupling products have been less explored. Besides some excellent work reported intermittently, reaction remains a significant challenge, particularly for preparing heterocyclic atropisomers. A concise but critical knowledge on this topic may further inspire researchers across various subdisciplines develop innovative practical solutions tackle problem. Therefore, Review aims summarize pioneering cross-couplings cover implementations via homogeneous heterogeneous catalysis during recent years. Most notably, use transition metals other than palladium also described.

Язык: Английский

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