The Doyle–Kirmse reaction is an organic reaction in which a metal carbene reacts with an allyl compound with transposition of the alkene and transfer of the electronegative group from the allyl onto the carbene carbon.
[1] The reaction was first reported by Wolfgang Kirmse [de] in 1968[2] and modified by Michael P. Doyle in 1981.
The reaction mechanism involves nucleophilic addition of the sulfur to the metal carbene formed from the diazoalkane followed by a Stevens-like rearrangement.
The reaction can also be catalyzed by iron,[4] palladium[5] silver,[6] and nickel.
[10] Using metal catalysts that have chiral ligands leads to stereoselectivity of the newly-formed carbon–carbon bond.