An enantioselective synthesis of P-stereogenic alkynylphosphine oxides through a cationic rhodium(l)/modified-binap complex catalyzed [2+2+2] cycloaddn. of sym. dialkynylphosphine oxides with 1,6-diynes was developed (binap = 2,2'-bis(diphenylphosphinyl)-1,1'-binaphthyl, Z = CH2, O, or N-sulfonamide). Furthermore, this method permits the synthesis of a C2-sym. P-stereogenic bis(alkynylphosphine oxide). A crystal structure of one product was detd. along with the abs. configuration of the phosphorus center. [on SciFinder(R)]
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