General Principles of Diastereoselective Reactions: Rigid Templates

Mulzer, Johann

Comprehensive Chirality 2012, 2, 9-44.

For many years diastereoselectivity was achieved primarily within conformationally rigid systems via appropriate substitution. With the advent of acyclic stereoselection and chiral catalysis things have changed, yet the idea of the rigid template is still vivid and fruitful. This chapter gives an overview of the past 30 years. It will be demonstrated that acetals, lactams, esters, aromatic and hydroaromatic compounds, and oxabicyclo- and bicycloolefins are useful templates to control onring stereocenters with high predictability. It will also be shown, how the template can be disconnected without endangering the, just acquired, stereogenic centers. In this way, a wide variety of complex chiral natural products have been prepared, for instance, polypropionates, carbohydrates, alkaloids, and terpenes.