转自：康龙化成
Synthesis of Thioethers viaNickel-Catalyzed Cross-Coupling of Aryl Halides with Ketene Dithioacetal
Baolong Xu, Shaowen Ling, Shuaichen Zheng, Xinyi Feng, Hui Liu, Yunhui Dong, Xinjin Li, Biqiong Hong,* and Feng-Gang Sun*
School of Chemistry and ChemicalEngineering, Shandong University of Technology, Zibo, Shandong 255049, P. R.China
College of Materials and ChemicalEngineering, Minjiang University, Fuzhou, Fujian 350108, P. R. China
—Org.Lett. 2025, 10.1021/acs.orglett.4c04692
Recommended by Chunlei Lu_ MC2
KEYWORDS: Ni catalysis (反应类型), C(sp2)− S (成键类型), Aryl halides (原料), Ketene dithioacetals (原料), Aryl-alkyl thioethers (产物), NiCl2(dme) (催化剂)
ABSTRACT: Herein,we present a nickel-catalyzed C−S cross coupling between aryl halides andketene dithioacetals under “base free” conditions without an exogenous ligand.By employing easily available ketene dithioacetals as sulfide donors, thisreaction affords a broad range of unsymmetrical alkyl-aryl sulfides withoutusing odorous and toxic thiols. The newly developed catalytic methodologyfeatures an excellent functional group tolerance, wide substrate scope, anddiverse downstream synthesis. Preliminary mechanism investigations reveal thata Ni(I)/Ni(III) catalytic cycle might be involved.
Strategies for Catalytic C−S BondFormation
Substrate Scope
Synthetic Applications
ProposedMechanism
Insummary, Prof. Feng-Gang Sun et al have reported a practical nickelcatalyzed C−S bond construction reaction via the cross-coupling of arylhalides with readily available ketene dithioacetals asthe thiol donors. A range of diverse aryl-alkyl thioethers areobtained in good yields under base-free reaction conditions in the absence ofan exogenous ligand. This catalytic transformation features excellent tolerancetoward different functional groups and general applicability. In addition,mechanistic experiments were conducted, which implicated a Ni(I)/Ni(III)pathway.
（转自：康龙化成）
