An efficient method for the construction of two distinct Caryl–Caryl bonds through the Ni‐catalyzed Suzuki–Miyaura cross‐coupling of phenols with arylboronic acids has been developed. This reaction proceeds through the in situ tosylation of phenols by using N,N‐ditosylaniline as the sulfonylating reagent, which is highly active, markedly stable, and easily prepared. The scope with respect to the coupling partners – phenols and boronic acids – is broad, and sensitive functional groups are tolerated. Phenols, especially those containing an unprotected amino group, which are generally problematic for coupling under conventional one‐pot conditions, are also viable substrates in this transformation.

The Pd-catalyzed homodimerization with respect to arylsulfonyl chlorides as an efficient method for the synthesis of biaryls has been developed. This desulfonylative reaction which was performed at reflux in 1,4-dioxane for 4 h under air afforded the desired products in good to excellent yields.

A nickel‐catalyzed approach for the synthesis of biaryl compounds from N,N‐disulfonylmethylamines and arylboronic acids has been developed. Instead of arenesulfonyl chlorides, various N,N‐disulfonylmethylamines were used as the aryl source through extrusion of SO2 to give cross‐coupling products in moderate to good yields.

Extrusion of SO2 from the starting amines affords the aryl source for the coupling reaction.

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