Trimethylzincate is known to react through conjugate addition to α,β-unsaturated ketones, but adds much faster to α,β-unsaturated esters at low temperatures. Since the intermediate zinc enolate behaves differently from that of dimethylcuprate, it offers scope for application in a partial synthesis of gibberellin A3. A second example involving vinylsulfones having an oxygen atom on the γ-carbon strongly directs incoming nucleophiles in conjugate addition mode. Heteroatom-directed conjugate addition (HADCA) provides very reactive carbanion intermediates leading to cyclobutane ring formation, necessary for synthesis of solanoeclepin A. An alternative reaction for the four-membered carbocyclic ring closure was explored to make a bond formation between the propargylic cation of Nicholas type and allyltrimethylsilane nucleophile of Hosomi–Sakurai type. This method allowed a formation of tricyclo[5.2.1.01,6]decene framework.