Catalytic Reductive Carbene Transfer Reactions

Efforts to develop catalytic carbene transfer reactions have largely relied on the use of diazo precursors. However, diazoalkanes are susceptible to undergoing violent exothermic decomposition unless they contain stabilizing substituents. Consequently, most synthetic methods are restricted to diazoacetates or related derivatives. In this Perspective, we describe an alternative approach to carbene transfer catalysis based on the generation of metal carbenoids from gem-dihaloalkanes and gem-dihaloalkenes. These precursors are readily available and stable in unsubstituted form or with a variety of donor and acceptor substituents. Using this approach, it is possible to design cyclopropanation reactions with non-stabilized carbenes, such as methylene, isopropylidene, and vinylidene. Furthermore, due to the distinct mechanistic pathways of these reactions, novel modes of cycloaddition can be carried out, including [4 + 1]-cycloadditions.