1535-32-6Relevant academic research and scientific papers
Site-Selective, Modular Diversification of Polyhalogenated Aryl Fluorosulfates (ArOSO2F) Enabled by an Air-Stable PdI Dimer
Mendel, Marvin,Kalvet, Indrek,Hupperich, Daniel,Magnin, Guillaume,Schoenebeck, Franziska
supporting information, p. 2115 - 2119 (2020/01/02)
Since 2014, the interest in aryl fluorosulfates (ArOSO2F) as well as their implementation in powerful applications has continuously grown. In this context, the enabling capability of ArOSO2F will strongly depend on the substitution pattern of the arene, which ultimately dictates its overall function as drug candidate, material, or bio-linker. This report showcases the modular, substrate-independent, and fully predictable, selective functionalization of polysubstituted arenes bearing C?OSO2F, C?Br, and C?Cl sites, which makes it possible to diversify the arene in the presence of OSO2F or utilize OSO2F as a triflate surrogate. Sequential and triply selective arylations and alkylations were realized within minutes at room temperature, using a single and air-stable PdI dimer.
Continuous flow synthesis of aryl aldehydes by Pd-catalyzed formylation of phenol-derived aryl fluorosulfonates using syngas
Hanselmann, Paul,Hone, Christopher A.,Hu, Guixian,K?ckinger, Manuel,Kappe, C. Oliver
, p. 22449 - 22453 (2020/07/03)
This communication describes the palladium-catalyzed reductive carbonylation of aryl fluorosulfonates (ArOSO2F) using syngas as an inexpensive and sustainable source of carbon monoxide and hydrogen. The conversion of phenols to aryl fluorosulfonates can be conveniently achieved by employing the inexpensive commodity chemical sulfuryl fluoride (SO2F2) and base. The developed continuous flow formylation protocol requires relatively low loadings for palladium acetate (1.25 mol%) and ligand (2.5 mol%). Good to excellent yields of aryl aldehydes were obtained within 45 min for substrates containing electron withdrawing substituents, and 2 h for substrates containing electron donating substituents. The optimal reaction conditions were identified as 120 °C temperature and 20 bar pressure in dimethyl sulfoxide (DMSO) as solvent. DMSO was crucial in suppressing Pd black formation and enhancing reaction rate and selectivity. This journal is
Nickel- and Palladium-Catalyzed Coupling of Aryl Fluorosulfonates with Aryl Boronic Acids Enabled by Sulfuryl Fluoride
Hanley, Patrick S.,Krasovskiy, Arkady L.,Ober, Matthias S.,Whiteker, Gregory T.,Kruper, William J.
, p. 5041 - 5046 (2015/09/15)
Herein are reported examples of the nickel- and palladium-catalyzed cross-coupling of aryl fluorosulfonates and aryl boronic acids. These reactions occur in good to excellent yields under mild conditions with excellent functional group compatibility employing either Pd(OAc)2 and inexpensive PPh3 or the inexpensive and readily available NiCl2(PCy3)2. Importantly, the in situ conversion of phenol derivatives to the corresponding aryl fluorosulfonate by reaction with sulfuryl fluoride and a base and subsequent cross-coupling to form biaryls in a single pot are described. The combination of inexpensive sulfuryl fluoride and efficient catalysts reported in these methodologies will enable economical Suzuki coupling of phenols in pharmaceutical and agrochemical processes.
