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Palladium-Catalyzed Cross-Couplings of Aryl Thianthrenium Salts with <i>N</i> -Tosylhydrazones for the Synthesis of 1,1-Diarylalkenes

Qian-Qian Fu, Sheng-Bo Zhang, Sang-Yong Song, Xue‐Qiang Chu, Hao Xu, Chengping Miao, Weidong Rao, Zhi‐Liang Shen

2025Organic Letters9 citationsDOI

Abstract

An efficient palladium-catalyzed cross-coupling of aryl thianthrenium salts with N -tosylhydrazones has been successfully developed, enabling the facile construction of a diverse array of valuable 1,1-diarylalkenes. The reactions proceeded well through C–S bond cleavage in the presence of Pd(OAc) 2 as a catalyst, Xphos as a ligand, and LiO t Bu as a base, showing both good substrate scope and wide functional group compatibility. Additionally, applications of the method in the late-stage diversification of bioactive complex molecules and gram-scale synthesis could be accomplished as well. Noteworthily, the one-pot, two-step reactions directly commencing from the utilization of arenes as starting materials with the aid of thianthrene S -oxide (TTSO) and Tf 2 O to in situ transform arenes into aryl thianthrenium salts followed by subsequent palladium-catalyzed couplings with N -tosylhydrazones could also be realized.

Topics & Concepts

ChemistryArylThianthreneCombinatorial chemistryFunctional groupMoleculeSubstrate (aquarium)Bond cleavageCleavage (geology)Organic chemistryReaction conditionsRetrosynthetic analysisScope (computer science)Group (periodic table)AnnulationIn situOrganic moleculesTandemCyclopropane Reaction MechanismsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques