Doyle-Kirmse reaction

An interesting Fe-catalyzed SN2 -like carbene insertion reaction using diazo compounds and allyl sulfides (the Doyle-Kirmse reaction) was reported by Carter and Van Vranken in 2000 [20], Various allyl thioethers were reacted with TMS-diazomethane in the presence of catalytic amounts of Fe(dppe)Cl2 to furnish the desired insertion products with moderate levels of stereocontrol [Equation (7.6), Scheme 7.14]. The products obtained serve as versatile synthons in organic chemistry, e.g. reductive desulfurization furnishes lithiated compounds that can be used in Peterson-type oleftnations to yield alkenes [Equation (7.7), Scheme 7.14] [21]. 

Scheme 7.14 Fe-catalyzed Doyle-Kirmse reaction. LDMAN = lithium l-(dimethylamino)naphthalenide [22].

Very recently, Davies and coworkers have reported a silver-catalyzed Doyle-Kirmse reaction of ally lie and propargylic sulfides with ethyl diazophenylacetate (35). A selection of examples was investigated providing the rearranged products, either homoallylic thioethers (76 —> 77, Scheme 8.14a) or allenyl thioethers (78 —> 79, Scheme 8.14b) in good yields, and with good overall scope.40... 

An elegant and efficient way for preparation of sulfonium ylides under mild conditions is the so-called Doyle-Kirmse reaction [25,26], which involves transition metal catalyzed decomposition of diazo compounds (usually a-diazocarbonyls) in the presence of sulfides. For the catalytic generation of matallocarbenes from diazo compounds, copper catalysts have traditionally been employed. More recently, rhodium and ruthenium compoimds were reported to be efficient catalysts, especially for the generation of sulfoniiun ylides [27-29]. 

The sulfur ylides 254 used in the stereoselective [2,3]-sigmatropic rearrangement are generated by copper(I)-catalyzed Doyle-Kirmse reaction of aryl sulfides 253 and diazo compounds bearing Oppolzer s camphor sultam auxiliary 252 in the presence of chiral diamine ligand S, S)-259 <05JA15016>. These intermediate ylides undergo spontaneous... 

In the presence of catalytic amounts of 31, an insertion into heteroatom-hydrogen S-H and N-H bonds, olefination of carbonyl groups, and Doyle-Kirmse reactions could be accomplished even in absence of ligands [102]. It should be noted that in the Doyle-Kirmse reaction a 2.5 moI% loading of the catalyst 31 is sufficient to afford in dichloromethane at 40°C good to excellent conversions. This transformation displays broad functional group tolerance. 

Rhodium(II) carbenoid intermediates are also useful. For example, carbene transfer reaction with allylic sulfides followed by [2,3]-sigmatropic rearrangement of the resulting sulfur ylides (Doyle-Kirmse reaction) gives furan-containing sulfides 133 in good yields (Scheme 19.32) [50]. In contrast, reaction with allylic compounds (R—H) or alcohols/amines/thiols/silanes (X—H) furnishes the 1,1-insertion products 134 or 135, respectively [51],... 

Catalytic Wittig-type and Doyle-Kirmse reactions have been achieved using diazo compounds as carbenoid sources in the presence of ferrate complex Bu4N[Fe(CO)3(NO)] as catalytic species this result highlights for the first time the potential of the electron-rich iron complex for activating diazo compounds to iron carbenoids. 

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