Enantioselective allylation is a highly used organic reaction to prepare chiral homoallylic alcohols and amines, which serve as important building blocks in the synthesis of a variety of natural products and pharmaceuticals.

An efficient bioinspired approach to the total synthesis of (±)-cafestol features a late-stage installation of the furan ring with a mild Au-catalyzed cycloisomerization. The Et₂AlCl-promoted aldehyde–ene cyclization and subsequent Friedel–Crafts reaction deliver a requisite tricyclic system in gram scale with high stereo- and regioselectivity. Moreover, a highly stereoselective SmI₂-mediated aldehyde–alkene radical cyclization furnishes the key bicyclo[3.2.1]octane skeleton to offer an advanced intermediate for the synthesis of other oxygenated ent-kaurene diterpenoids.

This review covers selected examples of point chirality-forming macrocyclizations in natural product total synthesis in the past three decades.