Allenes in Catalytic Asymmetric Synthesis and Natural Product Syntheses

Traditionally, transition metal-catalyzed enantioselective transformations rely on chiral ligands tightly bound to the metal to induce asymmetric product distributions. Here we report high enantioselectivities conferred by a chiral counterion in a metal-catalyzed reaction. Two different transformations catalyzed by cationic gold(I) complexes generated products in 90 to 99% enantiomeric excess with the use of chiral binaphthol-derived phosphate anions. Furthermore, we show that the chiral counterion can be combined additively with chiral ligands to enable an asymmetric transformation that cannot be achieved by either method alone. This concept of relaying chiral information via an ion pair should be applicable to a vast number of metal-mediated processes.

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.