C-O and C-C bond cleavage of α,β-unsaturated esters with the assistance of a gallane(pyridyl)iron complex.

Selective fragmentation of α,β-unsaturated esters into CC, CO, and OR fragments was investigated with the assistance of a gallane(pyridyl)iron complex Cp*(OC)Fe{(η-HGaMes)(η-2-CHN)} (1, Cp*: η-CMe, Mes: 2,4,6-MeCH). The reaction of 1 with methyl acrylate in CD afforded vinyliron complex Cp*(OC)Fe(CHCH) (2) and 4-membered GaO cyclic gallane [MesGaOMe] (3). The C-O and C-C bonds in -butyl acrylate were cleaved by the reaction with complex 1, producing complex 2 and pyridine-coordinated gallane Mes(-BuO)Ga(pyridine) (4). The selective bond cleavage reactions proceeded by the reactions of 1 with methyl methacrylate and methyl 2-butenoate to afford Cp*(OC)Fe(CRCHR) (R = Me, R = H (5), R = H, R = Me (6)) and 3. In contrast, compound 3 was formed in 11% NMR yield by the reaction of 1 with methyl 3-butenoate (β,γ-unsaturated ester), and complex mixtures of unidentified products were obtained by the reaction of 1 with methyl 4-pentenoate (γ,δ-unsaturated ester) and methyl propionate (saturated ester). The treatment of a cyclic ester, α-methylene-γ-butyrolactone, with 1 afforded a 4-membered GaO cyclic gallane dimer with Cp*(OC)FeC(CH)CHCH substituents on the oxygen atoms, namely [Cp*(OC)FeC(CH)CHCHOGaMes] (7). In addition, the bond cleavage reaction occurred by the reaction of 1 with allyl methyl ether to afford the (η-allyl)iron complex Cp*(OC)Fe(η-CHCHCH) (8) and 3. These results indicate that the existence of the -CC-C-OR fragment, regardless of the presence or absence of the CO group between the CC and OR fragments, is essential for the bond cleavage reaction.