Abstract
While the fundamental series of [2+2]cycloadditions and retro[2+2]cycloadditions that make up the pathways of ruthenium-catalysed metathesis reactions is well-established, the exploration of mechanistic aspects of alkene metathesis continues. In this Feature Article, modern mechanistic studies of the alkene metathesis reaction, catalysed by well-defined ruthenium complexes, are discussed. Broadly, these concern the processes of pre-catalyst initiation, propagation and decomposition, which all have a considerable impact on the overall efficiency of metathesis reactions.
Highlights
The metathesis reaction catalysed by well-defined homogeneous transition metal complexes has become a staple technique for the synthesis of a number of molecules
Astruc and Lloyd-Jones have discussed early work on elucidating this basic mechanism.[4,5]. This basic series of steps can be used to design a variety of processes, such as: ring-closing metathesis (RCM) in which a diene substrate forms a cycloalkene plus an alkene; cross-metathesis (CM) in which two alkenes are used to prepare two new alkenes; ring-opening metathesis polymerisation (ROMP) where a cyclic alkene is used to prepare a polymer; and acyclic diene metathesis (ADMET) where a diene substrate is polymerised to form a poly(alkene) chain (Scheme 1(b))
The initiation of a variety of pre-catalysts, key steps during the catalytic cycle, and the decomposition of metathesiscatalysts have all been explored by a range of researchers, using a number of techniques such as NMR spectroscopy, DFT studies, and mass spectrometry
Summary
While the fundamental series of [2+2]cycloadditions and retro[2+2]cycloadditions that make up the pathways of ruthenium-catalysed metathesis reactions is well-established, the exploration of mechanistic aspects of alkene metathesis continues. In this Feature Article, modern mechanistic studies of the alkene metathesis reaction, catalysed by well-defined ruthenium complexes, are discussed. These concern the processes of pre-catalyst initiation, propagation and decomposition, which all have a considerable impact on the overall efficiency of metathesis reactions
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