Chemo- and diastereoselective cyclopropanation of allylic amines and carbamates

A highly chemo- and diastereoselective protocol for the cyclopropanation of tertiary allylic amines with Shi’s carbenoid [CF3CO2ZnCH2I] is described. The high levels of diastereoselectivity observed in these reactions may be attributed to chelation of the nitrogen atom to the zinc reagent, which then transfers a methylene unit to the syn-face of the olefin. Furthermore, a stereodivergent protocol for the cyclopropanation of a range of allylic carbamates has been developed, which provides access to both diastereoisomers of the corresponding cyclopropanes with very high levels of diastereoselectivity: cyclopropanation with the Wittig–Furukawa reagent [Zn(CH2I)2] proceeds under chelation control to give the corresponding syn-product, whilst reaction with Shi’s carbenoid proceeds under steric control to give the corresponding anti-cyclopropane, in >95:5 dr in both cases.