Nickel- and Palladium-Catalyzed Coupling of Aryl Fluorosulfonates with Aryl Boronic Acids Enabled by Sulfuryl Fluoride
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.
Hanley, Patrick S.,Krasovskiy, Arkady L.,Ober, Matthias S.,Whiteker, Gregory T.,Kruper, William J.
Nickel- and Palladium-Catalyzed Cross-Coupling of Aryl Fluorosulfonates and Phosphites: Synthesis of Aryl Phosphonates
The synthesis of aryl phosphonates via nickel and palladium-catalyzed cross-coupling of aryl fluorosulfonates and phosphites is described. The products were obtained in good to excellent yields under mild conditions with broad functional group compatibility, employing either Pd(OAc)2 and DPEPhos or the readily available NiCl2(dme) and Xantphos as catalytic systems. Noteworthily, the present C(sp2)?P bond formation method could be applied to the direct conversion of phenols to the corresponding aryl phosphonates in one pot via reaction of phenols with SO2F2 and subsequent palladium-catalyzed cross-coupling.
Continuous flow synthesis of aryl aldehydes by Pd-catalyzed formylation of phenol-derived aryl fluorosulfonates using syngas
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
Hanselmann, Paul,Hone, Christopher A.,Hu, Guixian,K?ckinger, Manuel,Kappe, C. Oliver
p. 22449 - 22453
(2020/07/03)
A one-pot protocol for the fluorosulfonation and Suzuki coupling of phenols and bromophenols, streamlined access to biaryls and terphenyls
A one-pot protocol for the fluorosulfation and Suzuki coupling of phenols is described. The tandem reaction proceeds efficiently at room temperature, and various biaryls and biaryl fluorosulfates were obtained in good to excellent yields. Furthermore, biaryl fluorosulfates were utilized as versatile building blocks for the preparation of terphenyls. The Royal Society of Chemistry 2020.
Nickel-catalyzed carboxylation of aryl and heteroaryl fluorosulfates using carbon dioxide
The development of efficient and practical methods to construct carboxylic acids using CO2 as a C1 synthon is of great importance. Nickel-catalyzed carboxylation of aryl fluorosulfates and heteroaryl fluorosulfates with CO2 is described, affording arene carboxylic acids with good to excellent yields under mild conditions. In addition, a one-pot phenol fluorosulfation/carboxylation is developed.
Palladium Cross-Coupling Reactions of Aryl Fluorosulfonates: An Alternative to Triflate Chemistry
A new and efficient electrophilic partner for palladium(0)-catalyzed cross coupling is reported.Aryl fluorosulfonates are readily prepared in high yield by treatment of the appropriate phenol with fluorosulfonate anhydride.The palladium-catalyzed coupling reactions of these fluorosulfonates with vinyl- and aryltin reagents, as well as organozinc chlorides, takes place under mild conditions in a regio- and stereoselective manner.
Roth, Gregory P.,Fuller, Carl E.
p. 3493 - 3496
(2007/10/02)
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