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

Dalton Transactions Pub Date: 2021-10-22 DOI: 10.1039/D1DT03286K

Abstract

Selective fragmentation of α,β-unsaturated esters into C[double bond, length as m-dash]C, C[double bond, length as m-dash]O, and OR fragments was investigated with the assistance of a gallane(pyridyl)iron complex Cp*(OC)Fe{(η1-HGaMes2)(η1-2-C5H4N)} (1, Cp*: η5-C5Me5, Mes: 2,4,6-Me3C6H2). The reaction of 1 with methyl acrylate in C7D8 afforded vinyliron complex Cp*(OC)2Fe(CH[double bond, length as m-dash]CH2) (2) and 4-membered Ga2O2 cyclic gallane [Mes2GaOMe]2 (3). The C–O and C–C bonds in t-butyl acrylate were cleaved by the reaction with complex 1, producing complex 2 and pyridine-coordinated gallane Mes2(t-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)2Fe(CR1[double bond, length as m-dash]CHR2) (R1 = Me, R2 = H (5), R1 = H, R2 = 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 Ga2O2 cyclic gallane dimer with Cp*(OC)2FeC([double bond, length as m-dash]CH2)CH2CH2 substituents on the oxygen atoms, namely [Cp*(OC)2FeC([double bond, length as m-dash]CH2)CH2CH2OGaMes2]2 (7). In addition, the bond cleavage reaction occurred by the reaction of 1 with allyl methyl ether to afford the (η3-allyl)iron complex Cp*(OC)Fe(η3-CH2CHCH2) (8) and 3. These results indicate that the existence of the –C[double bond, length as m-dash]C–C–OR fragment, regardless of the presence or absence of the C[double bond, length as m-dash]O group between the C[double bond, length as m-dash]C and OR fragments, is essential for the bond cleavage reaction.

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