Directing Group Repositioning Strategy Enabled Site- and Enantioselective Addition of Heteroaromatic C–H Bonds to Acyclic Internal Alkenes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6861 - 6870

Published: March 14, 2023

Despite the notable advances achieved in Murai-type hydroarylations, highly enantioselective catalytic addition of native (hetero)arenes to internal alkenes remains a prominent challenge. Herein, we report directing group repositioning strategy, which enables iridium-catalyzed heteroarenes including furan, benzofuran, and thiophene enamides. The C-H bond at C2 position heteroarene is site-selectively cleaved added regioselectively β-position an enamide, affording valuable β-heteroaryl amide with high enantioselectivity. Mechanistic studies indicate that rate enantioselectivity are determined by separate elementary steps.

Language: Английский

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C–N Axially Chiral Heterobiaryl Isoquinolinone Skeletons Construction via Cobalt-Catalyzed Atroposelective C–H Activation/Annulation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(34), P. 6240 - 6245

Published: Aug. 18, 2023

Herein, the atroposelective construction of isoquinolinones bearing a C-N chiral axis has been successfully developed via Co-catalyzed C-H bond activation and annulation process. This conversion can be effectively carried out in an environmentally friendly oxygen atmosphere to generate target axially frameworks with excellent reactivities enantioselectivities (up >99% ee) absence any additives. Additionally, current protocol proved alternative approach for axial architectures fabrication under electrochemical conditions cobalt/Salox catalysis, this strategy allowed efficient atom-economical synthesis various mild reaction conditions.

Language: Английский

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Iridium-Catalyzed Branch-Selective and Enantioselective Hydroalkenylation of α-Olefins through C–H Cleavage of Enamides

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(38), P. 17351 - 17358

Published: Sept. 19, 2022

Catalytic branch-selective hydrofunctionalization of feedstock α-olefins to form enantioenriched chiral compounds is a particularly attractive yet challenging transformation in asymmetric catalysis. Herein we report an iridium-catalyzed hydroalkenylation through directed C–H cleavage enamides. This atom-economical addition process highly and enantioselective, delivering trisubstituted alkenes with allylic stereocenter. DFT calculations reveal the origin regio- enantioselectivity.

Language: Английский

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Construction of Non-Biaryl Atropisomeric Amide Scaffolds Bearing a C–N Axis via Enantioselective Catalysis

Molecules, Journal Year: 2022, Volume and Issue: 27(19), P. 6583 - 6583

Published: Oct. 4, 2022

The significant scaffold offered by atropisomeric amides with a C–N chiral axis has been extensively utilized for pharmaceuticals, agricultural science, and organic syntheses. As result, the field of atropisomer synthesis attracted considerable interest within chemistry communities. To date, range catalytic atroposelective approaches reported efficient construction these challenging scaffolds. However, greatly concise highly useful methodologies compounds, focusing on transition-metal, amine, phosphoric acid catalysis reactions, etc., are still desirable. Hence, it is indispensable to succinctly systematically present all such reports means disclosing mechanistic analysis application, as well challenges issues associated establishment atropisomers. In this review, we summarize development asymmetric synthetic strategies access non-biaryl atropisomers rotating around axis, including reaction methods, mechanism, late-stage transformations, applications.

Language: Английский

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One reaction – double stereoinduction: C–H activation as a privileged route towards complex atropisomeric molecules

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(53), P. 8159 - 8167

Published: Jan. 1, 2023

Expanding the importance of chirality and implementation stereogenic information within complex molecular design has recently reached a new level: innovative enantiopure scaffolds bearing multiple chiral elements.

Language: Английский

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