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The Doyle–Kirmse reaction is an organic reaction in which in the original scope an allyl sulfide reacts with trimethylsilyldiazomethane to form the homoallyl sulfide compound. The reaction was first reported by W. Kirmse in 1968 and modified by M.P. Doyle in 1981.
The Kirmse protocol required a copper salt. The reaction type is nucleophilic addition of sulfur to a metal carbene formed from the diazoalkane followed by a Stevens-like rearrangement.
Doyle expanded the scope of the reaction to include diazo compounds such as ethyl diazoacetate, allyl amines and allyl halides with rhodium catalysts such as Hexadecacarbonylhexarhodium. An example is the reaction of ethyl diazoacetate with allyl iodide:
The reaction can also be catalyzed by iron, palladium and silver Modifications using other carbenes are reported e.g. (2-furyl)carbenoids. With use of certain propargyl sulfides the reaction product is an allene.