Chiral aminophosphines derived from hydroxyproline and their application in allene-imine [4 + 2] annulation.

A robust synthetic route from L-hydroxyproline (L-Hyp) to phosphines has established an expandable library of six chiral aminophosphines, which were then applied to the phosphine-catalyzed [4 + 2] allene-imine annulation. The enantioinduction in the annulations-induced by a purely steric effect-were moderate (up to 57% ee). A switch of the reaction site from the γ- to the ß'-carbon atom of the allenoate was observed during the annulations performed using sterically demanding chiral phosphines.

Chiral aminophosphines as catalysts for enantioselective double-Michael indoline syntheses.

The bisphosphine-catalyzed double-Michael addition of dinucleophiles to electron-deficient acetylenes is an efficient process for the synthesis of many nitrogen-containing heterocycles. Because the resulting heterocycles contain at least one stereogenic center, this double-Michael reaction would be even more useful if an asymmetric variant of the reaction were to be developed. Aminophosphines can also facilitate the double-Michael reaction and chiral amines are more readily available in Nature and synthetically; therefore, in this study we prepared several new chiral aminophosphines. When employed in the asymmetric double-Michael reaction between ortho-tosylamidophenyl malonate and 3-butyn-2-one, the chiral aminophosphines produced indolines in excellent yields with moderate asymmetric induction.

Equilibrium between a vinylogous ylide and a phosphonium dienolate zwitterion: vinylogous Wittig olefination versus vinylogous aldol-type reaction.

This paper describes the equilibrium established between a phosphonium dienolate zwitterion and a vinylogous phosphorus ylide, and their reactions with aldehydes. The reactions between ethyl 2-methyl-2,3-butadienoate and various aldehydes occur through either a phosphonium dienolate or a vinylogous ylide intermediate, depending on the presence/absence of a Lewis acid and the nature of the phosphine. We observed a rare vinylogous Wittig olefination from the reaction between ethyl 2-methyl-2,3-butadienoate and an electron-deficient aromatic aldehyde in the presence of a stoichiometric amount of an electron-deficient triarylphosphine and a catalytic amount of a Lewis acid (e.g., BF(3)·Et(2)O). On the other hand, the use of triphenylphosphine, in the absence of a Lewis acid, facilitated vinylogous aldol addition, accompanied by a rare 1,2-aryl phosphorus-to-carbon migration.