Oxovanadium (V)-induced dl-selective oxidative coupling of (Z)-boron enolate was demonstrated to give the corresponding 2, 3-disubstituted 1, 4-diketone in a good yield. High selectivity (up to 94 [thin space (1/6-em)]:[thin space (1/6-em)] 6) was attained when the reaction was performed with VO (OPr-i) 2 Cl at− 30 C.