Diverse ortho-stannylbiaryls and teraryls have been synthesized by copper-catalyzed arylstannylation of arynes, in which the single or dual insertion of arynes into arylstannanes is precisely controllable by simply changing the equivalence of the aryne precursors employed.

A direct method for the synthesis of acridane derivatives based upon a 2:1 coupling reaction between arynes and imines was developed. The reaction proceeds through formation of transient aza‐ortho‐quinone methides arising from a net [2+2] cycloaddition between arynes and imines. Introduction of steric bulk into an imine carbon has proven to be vital for this facile coupling.

A carbon–carbon triple bond of arynes was found to undergo cyanostannylation with a tin cyanide under CuCN catalysis to afford diverse ortho‐cyanoarylstannanes in high yield. The copper catalyst was also effective for alkynylstannylation of arynes, and the resulting alkynylstannylated products were demonstrated to be convertible into biologically active compounds and a dye for dye‐sensitized solar cell.

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