Mechanistic and stereochemical aspects of the asymmetric cyclocarbonylation of 1,6-enynes with rhodium catalysts

Abstract

NMR and kinetic investigations of the cyclocarbonylation of 1,6-enynes with cationic rhodium(I) catalysts, modified with atropisomeric diphosphines, disprove the involvement of carbonyl species for 1,6-enyne activation; low-temperature catalysis, with molecular sieves as the carbon monoxide reservoir, is highly enantioselective (ee up to 97%).