NMR spectroscopy: a versatile tool for the investigation of organic reaction mechanisms and metabolomics analyses

Olefin metathesis has become a powerful tool for the formation of carbon-carbon bonds and, therefore, for the synthesis of a number of molecules. This progress was recognized in 2005 with the award of NOBEL Prize in Chemistry to Yves Chauvin, Robert Grubbs and Richard Schrock for their work in this area. While the series of [2+2]cycloadditions and retro[2+2]cycloadditions that make up the pathways of ruthenium-catalysed metathesis reactions is wellestablished, the exploration of mechanistic aspects of alkene metathesis is going on. At first, we reported the tetramerization of (E)-2,4-dimethoxycinnamic acid ω-undecenyl ester with ethereal BF3. The reaction gave three stereoisomers 1a, 1b, and 1c, which were assigned as the chair, cone, and 1,2-alternate conformations, respectively. Undecenyl resorc[4]arene 1a, which featured the simplest pattern of substituent, was submitted to olefin metathesis using the second generation Grubbs complex as the catalyst. Depending on the reaction conditions, different products were isolated: a bicyclic alkene 2a, a linear dimer 3a, and a cross-linked homopolymer P1a. Moreover, we detected for the first time the formation of a ruthenium-carbene resorc[4]arene complex during the metathesis reaction of resorc[4]arene olefin 2a with the first generation Grubbs catalyst in CDCl3. We developed an NMR analytical protocol which proved capable of yielding both qualitative and quantitative information. In the first case, we were able to identify the complex 3a[Ru] as a key intermediate in the ROM-CM sequence of reactions, giving us a definitive proof of the previously hypothesized mechanism. As a further feedback of the pathway, we performed a quantitative analysis using benzene in the place of CDCl3, due to the poor stability of the catalyst in such a solvent. The reaction allowed the isolation of decomposition products of the ruthenium-carbene-resorc[4]arene complex 2a[Ru] such as compound 4a, which, due to the presence of still reactive alkene functions, proved to behave as propagating alkylidene species leading to further decomposition products.