Previous studies showed that oxidation of α-olefins with monometallic catalysts containing chiral diphosphines and diamines gave chlorohydrins with poor to good enantioselectivites (28–82 % ee). The present studies demonstrate that bimetallic catalysts containing a β-triketone and bridging chiral diphosphine and diamines are excellent catalysts for this reaction giving enantioselectivites considerably higher than the monometallic catalysts. Enantioselectivities were more than 50 % for most olefins tested. The highest optical purities were 94 % ee for propene and 93 % ee for allylphenyl ether. A useful feature of this asymmetric synthesis is the fact it is a net air oxidation.