The organocatalytic enantioselective decarboxylative addition of malonic acids half thioesters to isatins using a squaramide catalyst afforded the products with high enantioselectivity. These products are key intermediates in the synthesis of 3‐substituted 3‐hydroxy‐2‐oxindole derivatives. The first enantioselective synthesis of (−)‐flustraminol B has been accomplished.