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.

An unprecedented AlCl3-promoted formal [2 + 3]-cycloaddition of 1,1-cyclopropanes with readily available N-benzylic sulfonamides has been developed. Experimental evidence supports an unusual mechanism wherein the donor-acceptor cyclopropane serves as a source of 2-styrylmalonate rather than the "classical" 1,3-dipole. A broad range of 1,1-cyclopropanediesters undergo a carbocation-initiated cyclization reaction with N-benzylic sulfonamides to afford highly functionalized Indane derivatives in a fast and high-yielding procedure.

A La(OTf)3‐catalyzed domino method has been developed to synthesize the cis‐1,4‐benzoxazine derivatives from 2‐furylcarbinols 1 and o‐aminophenol derivatives, by a Piancatelli/C–N coupling/Michael addition process. A wide array of substrates could be used to give the desired products in good yields. Since this method involves simple reaction conditions and short reaction times, and has a broad substrate scope, it is particularly attractive for the efficient development of libraries of biologically relevant 1,4‐benzoxazine derivatives. Furthermore, a similar strategy was also successfully applied to form 1,2,3,4‐tetrahydroquinoxaline derivatives from 1 and N‐substituted o‐diaminobenzenes.

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A new and efficient protocol for the preparation of 4,5-diaminocyclopent-2-enones via the reaction of N-sulfonylimine with secondary amines, with p-toluenesulfonamide acting as a leaving group, is presented. In addition, p-toluenesulfonamide worked well as a catalyst even with a catalytic amount for the reaction of 2-furaldehyde and secondary amines to afford the corresponding products in higher yields.