Abstract An asymmetric decarboxylative 1, 4-addition of malonic acid half thioesters (MAHTs) to 2-aryl-substituted vinyl sulfones has been developed, yielding adducts with excellent enantioselectivity (up to 97% ee). In view of tuning pK a values, a quinine-based benzyl-substituted thiourea was designed and demonstrated as the most efficient catalyst. The enantioselective synthesis of 3-monofluorinated analogues of 3-methyl indanone and ...