Catalytic Asymmetric [4+2] Annulation Initiated by an Aza-Rauhut-Currier Reaction: Facile Entry to Highly Functionalized Tetrahydropyridines

The development of some new synthetic reactions derived from nucleophilic addition of phosphines to electron-deficient carbon-carbon triple bonds is described. These reactions show that the phosphine plays the role of a nucleophile as well as an excellent leaving group. The central problem is to generate a 1,3-dipole from alkynoates or allenoates (2,3-butadienoates) by interaction with various phosphines. This study illuminates the unusual phenomena and shows how this understanding allows control of the reaction.

Nucleophilic phosphine catalysis has proven to be a powerful tool in organic synthesis, which can provide easy access to cyclic, bicyclic or polycyclic carbocycles and heterocycles. Owing to their comparatively strong and readily tunable nucleophilicity, phosphines can be easily tailored to efficient annulation reactions with good control over reaction selectivity. This has resulted in a tremendous increase in their scope and in a concomitant number of reports where phosphine-triggered annulation reactions occur. This tutorial review summarizes the recent achievements in this area.