No abstract

The Pd-catalyzed asymmetric [4+2] cycloaddition reaction of an aliphatic 1,4-dipole with singly activated electron-deficient alkenes is realized for the first time, enabled by using a newly developed benzylic substituted P,N-ligand, affording tetrahydropyrans having three continuous chiral centers in high yields with high diastereo- and enantioselectivities. The rational transition states of the reaction as well as the role of the benzylic chiral center are proposed.

The activated alkynes have been used successfully for the first time as the dipolarophile in the palladium-catalyzed asymmetric (3 + 2) cycloaddition, affording highly functionalized cyclopentenes in good to high yields with high chemoselectivities and good to high enantioselectivities. The introduction of an additional carbonyl group at the α-position of the alkynyl esters is the key to activating the carbon–carbon triple bond. The reaction process was investigated, and an inverse process of Pd-catalyzed (3 + 2) cycloaddition was observed.