Lewis base-promoted rearrangement of allylic cyanohydrins: construction of functionalized nitriles bearing 1,3-diketone moieties.

A novel Lewis base-promoted rearrangement of allylic cyanohydrins has been developed, in which the cyano group was rearranged, directly coupled with the generation of new functional groups. This protocol provides a unique and facile way to prepare highly functionalized nitriles bearing 1,3-diketone moieties under mild reaction conditions. Furthermore, the synthetic transformations of the functionalized products have also been demonstrated.

Copper-Promoted Cyclization of α-Amino Nitrile-Tethered Enynes: Controllable Synthesis of 3-Azabicyclo[4.1.0]hepta-2,4-dienes and 4,5-Dihydro-3H-azepines.

The first example of Cu-promoted cyclization of α-amino nitrile-tethered enynes incorporating an electron-deficient alkene component is described. A wide range of functionalized 3-azabicyclo[4.1.0]hepta-2,4-dienes and 4,5-dihydro-3H-azepines were prepared efficiently in a controllable manner. Moreover, the diverse cascade process enables efficient incorporation of tertiary amine moieties under mild reaction conditions. A possible reaction pathway is proposed on the basis of a series of control experiments.