The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxy)enoates having pendant iodo-and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from a formal anti-selective carbo-zincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.