Construction of Di(hetero)arylmethanes Through Pd‐Catalyzed Direct Dehydroxylative Cross‐Coupling of Benzylic Alcohols and Aryl Boronic Acids Mediated by Sulfuryl Fluoride (SO₂F₂)

Abstract

A practical Pd‐catalyzed direct dehydroxylative coupling of (hetero)benzylic alcohols with (hetero)arylboronic acids for the constructions of di(hetero)arylmethane derivatives under SO2F2 was described. This new method provided a strategically distinct approach to di(hetero)arylmethane derivatives from readily available and abundant benzylic alcohols under mild condition.

Synthesis of Arylethylamines via C(sp3)–C(sp3) Palladium-Catalyzed Cross-Coupling

“…Cross-couplings of 3-picolyl-derived ammonium salts have been previously reported. 27 Scheme 4. Formation of betaine 4a followed by addition of palladium catalyst, under optimized conditions afforded full conversion to arylethylamine 3a, suggesting oxidative addition occurs from ammonium-containing 4a.…”

Sequential Selective C−H and C(sp3)−+P Bond Functionalizations: An Entry to Bioactive Arylated Scaffolds

“…Next, we explored the direct amination of the C(sp 3 )À + PPh 3 bond (Figure 3A)t og ive benzhydrylamines.T hese compounds (e.g., 5-7)h ave long been considered building blocks of many important drugs,s uch as bifonazole (2a), [16] chlorcyclizine (2b), [17] meclizine (2c), [18] and buclizine (2d). [18] Although many powerful methods exist for the synthesis of benzhydrylamines,t hese approaches typically involve multistep protocols,h arsh reaction conditions,p refunctionalized starting materials,h armful reagents,o rt he use of toxic alkylating reagents or reactive organometallic species.…”

SO2F2‐Promoted Dehydroxylative Fluorination of Alcohols

“…And the fluorosulfate functional group (−OSO 2 F) can be used for a variety of transformations due to the remarkable stability of the sulfate connector to hydrolysis. Recently, Qin and co‐workers reported applications of SO 2 F 2 in chemical transformations, including heterocycles, [14] nitriles, [15] diarylmethanes, [16] arylcarboxylic acids, [17] alkynes, [18] and amides [19] . In 2013, the dehydroxyfluorination of the amino alcohol (the amino group is protected with a phthaloyl group) with SO 2 F 2 in the presence of Et 3 N to form the corresponding alkyl fluorides has been disclosed [20] .…”