Rapidly accumulating evidence shows the value of asymmetric Diels-Alder and ene reactions for the syntheses of enantiomerically pure molecules. This article presents a systematic and critical treatment of various stereoface-differentiating principles, including very recent spectacular advances. The chiral information is mainly provided by covalently bound auxiliaries, some of which are crystalline, inexpensive, and readily available from naturally occurring monoterpenes, hydroxy acids, amino acids, steroids, and sugars. Non-destructive transfer of chirality leads to the efficient creation of up to four chiral centers with predictable relative and absolute configurations. Regenerative cleavage of the auxilary group from the diastereomerically pure adducts furnishes a range of polyfunctional, optically pure building blocks. Their synthetic potential is illustrated by strategic applications to the syntheses of physiologically interesting, chiral natural products such as prostaglandins, antibiotics, terpenoids, shikimic acid, alkaloids, and kainoids.

Up to four asymmetric centers with predictable relative and absolute configuration can be created in one step using the asymmetric Diels-Alder reaction. Its potential is manifested, above all, in the synthesis of natural products, e.g. (−)-β-santalene 1, a constituent of sandalwood.