Synthesis of Tetrasubstituted Olefins Through Nucleophilic Addition–Oxidation Cascade Reaction via Base Catalysis

ChemistrySelect, Год журнала: 2025, Номер 10(20)

Опубликована: Май 1, 2025

Abstract An efficient addition‐oxidation cascade reaction has been developed between α‐ aminomaleimide and vinylogous oxindole with strong electron‐withdrawing group (‐CN or ‐COCOOR), enabling the synthesis of a diverse array tetrasubstituted olefins high yields exceptional diastereoselectivities (up to 98% yield up >20:1 Z / E ). The tolerance free amine investigated, results demonstrated that most could not affect nucleophilic addition step except for aliphatic primary amines. Mechanistic investigations confirmed formation an intermediate (detected by HRMS), providing key insights into pathway. Futher study on thermodynamic calculations indicated stereoselectivity oxidation was promoted generating more thermodynamically stable ‐tetrasubstituted olefins. reactions also proceeded smoothly large scale, further proving their synthetic value. This strategy, in authors’ previous work, facilitates substrate‐directed switchable chemodivergent transformations, enhancing flexibility broadening potential applications.

Язык: Английский

Stereocontrolled Construction of Spirooxindole-Containing 5,6,7,8-Tetrahydropyrrolo[1,2-a]pyridine via Michael/Friedel–Crafts Domino Reaction Promoted by Secondary Amine-Squaramide

Organic Letters, Год журнала: 2024, Номер 26(11), С. 2152 - 2157

Опубликована: Март 8, 2024

An asymmetric Michael/Friedel–Crafts cascade reaction with Morita–Baylis–Hillman (MBH) nitroallylic esters and 3-pyrrolyloxindoles has been developed for the stereoselective construction of spirooxindole-containing tetrahydroindolizines. A range tetracyclic scaffolds possessing three consecutive chiral centers, including an all-carbon quaternary stereocenter, were generated in 53–85% isolated yields high diastereoselectivities enantiopurities (≥3:1 dr, 50–98% ee). newly synthesized bifunctional secondary amine/squaramide organocatalyst was demonstrated to exhibit better stereochemical control than their tertiary analogues.

Язык: Английский

Synthesis of Aza‐Bicyclic Maleimide Skeleton by Addition‐Ring Opening Cascade Reaction of Vinylogous Oxindole

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(20)

Опубликована: Апрель 1, 2024

Abstract An efficient method has been developed to facilitate the addition‐ring opening cascade reaction of vinylogous oxindole, resulting in synthesis a variety aza‐bicyclic maleimide derivatives with high yields and exceptional diastereoselectivities. Furthermore, product could be effectively easily transformed into difluoromethylenecyclohexane skeleton through dehydrofluorination process. This methodology demonstrates significant potential for skeleton, which possesses biological or pharmaceutical activity.

Язык: Английский