It was established that a cationic rhodium(I)/H8-BINAP complex is able to catalyze a [2+2+2] cycloaddn. of diynes with carbodiimides and carbon dioxide under ambient conditions. Enantioselective variants and regioselective variants of these reactions are also disclosed. Under optimized conditions the synthesis of the target compds. was achieved using N,N'-[(methane)tetrayl]bis[4-methylbenzenamine], N,N'-[(methane)tetrayl]bis[cyclohexanamine] (i.e., dicyclohexylcarbodiimide) and diynes, such as 2,2-bis(2-propynyl)propanedioic acid esters, 4-methyl-N,N-bis(2-propynyl)benzenesulfonamide. 3,3-bis(2-butynyl)-2,4-pentanedione as starting materials, bis[(1,2,5,6-ﾎｷ)-1,5-cyclooctadiene]rhodium tetrafluoroborate(1-) as a catalyst and 1,1'-(5,5',6,6',7,7',8,8'-octahydro[1,1'-binaphthalene]-2,2'-diyl)bis[1,1-diphenylphosphine] (H8-BINAP) as a ligand. [on SciFinder(R)]
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