The Maitland-Japp reaction has been extended to the synthesis of highly functionalised dihydropyran-4-ones. These dihydropyran-4-ones can in turn be converted stereoselectively into tetrahydropyran-4-ones with tertiary and quaternary stereocentres via the one-pot addition of hydride or carbon nucleophiles and trapping with carbon electrophiles. The utility of this method is demonstrated by prov...

β-Isocupreidine (β-ICD) catalyzed asymmetric [4 + 2] cycloaddition of β,γ-unsaturated α-ketoesters with allenic esters afforded ester-substituted functionalized dihydropyran derivatives in high yields along with high enantioselectivities under mild conditions.

Concise cascade reactions of pyruvates with aldehydes that generate functionalized dihydropyran derivatives in one pot have been developed. The products, dihydropyrans, were further concisely transformed to various molecules.

The scope of highly enantioselective and diastereoselective Michael additions of enolsilanes to unsaturated imide derivatives has been developed with use of [Cu((S,S)-t-Bu-box)](SbF6)2 (1a) as a Lewis acid catalyst. The products of these additions are useful synthons that contain termini capable of differentiation under mild conditions. Michael acceptor pi-facial selectivity is consistent with ...

Highly efficient DABCO-catalyzed [4 + 2] cycloaddition of β,γ-unsaturated α-ketophosphonates or β,γ-unsaturated α-ketoesters with allenic esters gives the corresponding highly functionalized tetrahydropyran and dihydropyran derivatives in good to excellent yields and moderate to good regioselectivities under mild conditions.

The highly enantioselective dienamine-mediated formation of 5-bromo-6-(trifluoromethyl)-3,4-dihydro-2H-pyrans from α,β-unsaturated aldehydes and α-bromo-(trifluoromethyl)-enones employing a C2-symmetric aminocatalyst is described. The products are demonstrated to be applicable in coupling reactions directly onto the ring, thereby granting access to a broad scope of highly substituted 6-(trifluo...