We have developed the Rh + /H 8 -binap-catalyzed chemo-, regio-, diastereo-, and enantioselective intermolecular [2+2+2] cycloaddition of three unsymmetric 2π components. Thus, two arylacetylenes react with a cis-enamide to yield a protected chiral cyclohexadienylamine. Moreover, replacing one arylacetylene with a silylacetylene enables the [2+2+2] cycloaddition of three distinct unsymmetric 2π components. These transformations proceed with excellent selectivity (complete regio-and diastereoselectivity and up to > 99 % yield and > 99 % ee). Mechanistic studies suggest the chemo-and regioselective formation of a rhodacyclopentadiene intermediate from the two terminal alkynes.

We have developed the Rh + /H 8 -binap-catalyzed chemo-, regio-, diastereo-, and enantioselective intermolecular [2+2+2] cycloaddition of three unsymmetric 2π components. Thus, two arylacetylenes react with a cis-enamide to yield a protected chiral cyclohexadienylamine. Moreover, replacing one arylacetylene with a silylacetylene enables the [2+2+2] cycloaddition of three distinct unsymmetric 2π components. These transformations proceed with excellent selectivity (complete regio-and diastereoselectivity and up to > 99 % yield and > 99 % ee). Mechanistic studies suggest the chemo-and regioselective formation of a rhodacyclopentadiene intermediate from the two terminal alkynes.