Empowering Diastereoselective Cyclopropanation of Unactivated Alkenes with Sulfur Ylides through Nucleopalladation

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

Regio- and stereoselective cyclopropanation of unactivated alkenes under mild conditions remains a challenging yet fundamental transformation. We present versatile palladium(II)-catalyzed method for the diastereoselective alkenyl amines acids, which leverages nucleopalladation mechanism unique ambiphilic reactivity sulfur ylides. This Pd(II)/Pd(IV) catalytic protocol selectively delivers anti-cyclopropanes allylamines with removable isoquinoline-1-carboxamide auxiliary, while enabling excellent syn-selectivity acid derivatives containing 2-(aminomethyl)pyridine derivative as directing group. The is operationally simple scalable, features wide substrate generality, also effective in presence various medicinally relevant scaffolds. cyclopropane products were further transformed into 1,2,3-trifunctionalized cyclopropanes engaged an aza-Piancatelli reaction, introducing additional molecular complexity. DFT studies performed to shed light on reaction origins observed stereoselectivity.

Language: Английский

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Regioselective and Chemodivergent Synthesis of Azulenolactones and Azulenolactams from Rhodium(III)‐Catalyzed Reactions of Azulenecarboxamides with Sulfoxonium Ylides

Advanced Synthesis & Catalysis, Journal Year: 2020, Volume and Issue: 363(2), P. 512 - 524

Published: Nov. 4, 2020

Abstract A regioselective and chemodivergent synthetic approach for azulenolactones azulenolactams as a new scaffold was demonstrated through Rh(III)‐catalyzed reaction of N ‐methoxyazulene‐1‐carboxamides with sulfoxonium ylides. Sulfoxonium ylides that act precursor secondary carbene described, leading to the selective formation bearing two substituents on newly introduced double bond. This method functionalization less reactive 2‐position azulene overcome natural reactivity. magnified image

Language: Английский

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Recent Advances on Synthetic Methodology Merging C–H Functionalization and C–C Cleavage

Molecules, Journal Year: 2020, Volume and Issue: 25(24), P. 5900 - 5900

Published: Dec. 13, 2020

The functionalization of C–H bonds has become a major thread research in organic synthesis that can be assessed from different angles, for instance depending on the type catalyst employed or overall transformation is carried out. This review compiles recent progress synthetic methodology merges along with cleavage C–C bonds, either intra- intermolecular fashion. manuscript organized two main sections according to substrate which bond takes place, basically attending scission strained unstrained bonds. Furthermore, related works have been grouped basis mechanistic aspects transformations are out, i.e.,: (a) classic transition metal catalysis where organometallic intermediates involved; (b) processes occurring via radical generated through use initiators photochemically; and (c) reactions catalyzed mediated by suitable Lewis Brønsted acid bases, molecular rearrangements take place. Thus, throughout wide range approaches show combination single operations serve as platform achieve complex skeletons straightforward manner, among them interesting carbo- heterocyclic scaffolds.

Language: Английский

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Recent advances in synthesis of isocoumarins: An overview

Tetrahedron, Journal Year: 2023, Volume and Issue: 150, P. 133740 - 133740

Published: Nov. 12, 2023

Language: Английский

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Iridium-catalyzed arylation of sulfoxonium ylides and arylboronic acids: a straightforward preparation of α-aryl ketones

Organic Chemistry Frontiers, Journal Year: 2020, Volume and Issue: 7(14), P. 1802 - 1808

Published: Jan. 1, 2020

A highly efficient iridium(iii)-catalyzed arylation coupling of sulfoxonium ylides with arylboronic acids to generate α-aryl ketones has been established for the first time.

Language: Английский

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