|
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.〔''Name reactions and reagents in organic synthesis'' Bradford P. Mundy,Michael G. Ellerd,Frank G. Favaloro〕 The reaction was first reported by W. Kirmse in 1968 〔Kirmse, W. and Kapps, M. (1968), ''Reaktionen des Diazomethans mit Diallylsulfid und Allyläthern unter Kupfersalz-Katalyse''. Chemische Berichte, 101: 994–1003. 〕 and modified by M.P. Doyle in 1981.〔''Highly effective catalytic methods for ylide generation from diazo compounds. Mechanism of the rhodium- and copper-catalyzed reactions with allylic compounds'' Michael P. Doyle, William H. Tamblyn, Vahid Bagheri J. Org. Chem., 1981, 46 (25), pp 5094–5102 〕 Doyle-Kirmse reaction 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: Doyle diazo compound reaction The reaction can also be catalyzed by iron,〔''Iron-Catalyzed Doyle−Kirmse Reaction of Allyl Sulfides with (Trimethylsilyl)diazomethane'' David S. Carter and David L. Van Vranken Org. Lett., 2000, 2 (9), pp 1303–1305 〕 palladium 〔''Palladium-catalyzed insertion reactions of trimethylsilyldiazomethane'' Kevin L. Greenman, David S. Carter and David L. Van Vranken Tetrahedron Volume 57, Issue 24, 11 June 2001, Pages 5219-5225 〕 and silver 〔''Silver-catalysed Doyle–Kirmse reaction of allyl and propargyl sulfides'' Paul W. Davies, Sébastien J.-C. Albrecht and Giulio Assanelli Org. Biomol. Chem., 2009, 7, 1276-1279 〕 Modifications using other carbenes are reported e.g. (2-furyl)carbenoids.〔''Doyle−Kirmse Reaction of Allylic Sulfides with Diazoalkane-Free (2-Furyl)carbenoid Transfer'' Yumiko Kato,, Koji Miki,, Fumiaki Nishino,, Kouichi Ohe, and, Sakae Uemura Organic Letters 2003 5 (15), 2619-2621 〕 With use of certain propargyl sulfides the reaction product is an allene.〔〔''Iron-Catalyzed Reaction of Propargyl Sulfides and Trimethylsilyldiazomethane'' Rosalind Prabharasuth and, David L. Van Vranken The Journal of Organic Chemistry 2001 66 (15), 5256-5258 〕 ==References== 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「Doyle–Kirmse reaction」の詳細全文を読む スポンサード リンク
|
