An asymmetric intramolecular Cannizzaro reaction of aryl and alkyl glyoxals with alcohols has been realized with an unprecedented high level of enantioselectivity, on the basis of a newly developed congested TOX ligand and a gradual liberation protocol of active glyoxals from glyoxal monohydrates. Preliminary results suggested a mechanism of enantioselective addition of alcohols to glyoxals contributing most to the stereoselectivity, other than by the dynamic kinetic resolution of hemiacetal intermediates.

An efficient synthetic approach to benzoheterocycles has been developed based on the hydrolysis of key ylide intermediates in a tandem reaction, upon which a variety of 3-alkylidene dihydrobenzofurans and related benzoheterocyclic products can be obtained in high yields with excellent Z/E selectivity.

With the mediation of phosphine, the direct intramolecular coupling of two electrophiles – alkyl halides with electron-deficient olefins – has been successfully realized in an intramolecular conjugate addition manner. The reaction provides a new approach for the synthesis of chromans and relevant analogues.

With the mediation of phosphine, the direct intramolecular coupling of two electrophiles – alkyl halides with electron-deficient olefins – has been successfully realized in an intramolecular conjugate addition manner. The reaction provides a new approach for the synthesis of chromans and relevant analogues.