This work concerns the Mg(OMe)2 promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters with TMEDA as an additive. The isomerization proceeded under mild conditions and afforded γ-keto esters in high yield (up to 96%) within 2 h. Both (Z)- and (E)-γ-hydroxy-α,β-alkenoic esters were tolerated under the reaction conditions. This transformation involves the in situ formation of a dienolate intermediate from the easily accessible γ-hydroxy-α,β-alkenoic ester. The in situ generated dienolate can react with benzaldehyde and undergo a practical, useful tandem allylic isomerization-Aldol reaction to afford more functionalized compounds.

A highly diastereoselective annulation of simple aldehydes and 5-alkenyl thiazolones, via oxidative NHC catalysis has been developed. This strategy provides facile access to a diverse library of functionalized chiral thiazolo pyrones. Aerobic oxygen can also be applied as a secondary oxidant to avoid the use of stoichiometric organic or inorganic oxidants.

This work concerns the asymmetric additions of benzothiazole to a variety of N-tert-butanesulfinyl imines with excellent diastereoselectivities (d.r. up to >99:1). Amino alkoxyl lithium was the key additive to obtain the excellent diastereoselectivity. More functionalized 4-methyl-5-vinyl thiazole and alkyl imines which can isomerize to enamines are also compatible substrates to the present protocol.

A highly diastereoselective annulation of simple aldehydes and 5-alkenyl thiazolones, via oxidative NHC catalysis has been developed. This strategy provides facile access to a diverse library of functionalized chiral thiazolo pyrones. Aerobic oxygen can also be applied as a secondary oxidant to avoid the use of stoichiometric organic or inorganic oxidants.

This work concerns the Mg(OMe)2 promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters with TMEDA as an additive. The isomerization proceeded under mild conditions and afforded γ-keto esters in high yield (up to 96%) within 2 h. Both (Z)- and (E)-γ-hydroxy-α,β-alkenoic esters were tolerated under the reaction conditions. This transformation involves the in situ formation of a dienolate intermediate from the easily accessible γ-hydroxy-α,β-alkenoic ester. The in situ generated dienolate can react with benzaldehyde and undergo a practical, useful tandem allylic isomerization-Aldol reaction to afford more functionalized compounds.