Cationic Rhodium(I)/BINAP-type bisphosphine complexes: Versatile new catalysts for highly chemo-, regio-, and enantioselective [2+2+2] cycloadditions

Our research group was the first to discover that cationic rhodium(I)/BINAP-type bisphosphine complexes are versatile new catalysts for highly chemo-, regio-, and enantioselective [2+2+2] cycloadditions. The high chemo- and regioselectivity of these cycloadditions enabled efficient catalytic synthesis of substituted benzenes, cyclophanes, and nitrogen heterocycles. Furthermore, enantioselective variants of these cycloadditions were also developed that realized efficient catalytic constructions of axial, planar, central, and spiro chirality. 1 Introduction 2 Chemo- and Regioselective [2+2+2] Cycloadditions 2.1 [2+ 2-12] Cycloaddition of Terminal Alkynes 2.2 [2-11 2-12] Cycloaddition of Two Different Alkynes 2.3 [2-2+2] Cycloaddition of alpha,omega)-Diynes with Alkynes 2.4 [2 +2+21 Cycloaddition of Alkynes with Isocyanates, Isothiocyanates, and Carbon Disulfide 2.5 [2+2-12] Cycloaddition of Alkynes with Nitriles 3 Enantioselective [2+2+21 Cycloadditions 3.1 Construction of Axial Chirality 3.2 Construction of Planar Chirality 3.3 Construction of Central Chirality 3.4 Construction of Spiro Chirality 4 Summary