Synthesis of 1,5-Diamino-Substituted 1,3-Dienes via Rhodium(II)-Catalyzed Tandem Reactions of 1-Cyclopropylethylarenes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

Herein, (E,E)-1,5-diamino-1,3-dienes are stereoselectively synthesized from substituted aryl derivatives via a rhodium(II)-catalyzed C(sp3)-H functionalization involving cascade of cyclopropane ring expansion, cyclobutene formation, to 1,3-diene conversion, and regioselective diamination. Mechanistic studies show this one-pot process proceeds through hydrogen atom transfer (HAT), radical-polar crossover (RPC), elimination, electrocyclic ring-opening, radical addition, underscoring rhodium(II)'s role in radical-mediated catalysis beyond traditional rhodium(II) nitrenoid chemistry.

Language: Английский

A General Medium-to-Large Sized Ring Synthesis Enabled by Copper-Catalyzed Difluoroalkylamidation Cyclization of Alkynes

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

This paper describes a novel coordinating activation strategy that enables the synthesis of medium-to-large sized rings (11-17 members) via an unprecedented difluoroalkylamidation cyclization alkynes. method provides efficient platform for accessing skeleton-diverse difluoroalkyl-containing cyclic enamides with complete regio- and stereoselectivity. The protocol features broad substrate compatibility, functional group tolerance, ease use at dilution concentrations (50 mM) are not high. Moreover, synthetic utility this difunctional is underscored by its application in late-stage modification complex molecules. Additionally, click reaction facilitates derivation alkynyl-substituted products, demonstrating methodology's potential biological sciences.

Language: Английский

Electrochemical 1,5-chlorosulfonylation and 1,5-hydrosulfonylation of vinylcyclopropanes

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(19), P. 5564 - 5572

Published: Jan. 1, 2024

This study reports the electrochemical reaction of vinylcyclopropanes with sulfonyl chlorides, resulting in 1,5-hydrosulfonylation and 1,5-chlorosulfonylation.

Language: Английский