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Ruthenium (II) - catalysed enyne carbocyclization reactions

Abstract : This dissertation focuses on cyclization reactions of 1,6-enynes involving ruthenium catalysts. Three different types of cyclization were developed from readily available precursors, such as 1,6-enynes and alkynes. In one application, a novel ruthenium-catalyzed hydroalkynylative cyclization of 1,6-enynes using terminal alkynes as co-reactants was explored. This reaction provides and entry to five-membered rings featuring an exocyclic 1,5-enyne motif. A neutral electron-rich ruthenium complex Cp*Ru(cod)Cl proved to be the catalyst of choice for these transformations. In another application, using the same complex, the ruthenium-catalyzed [2+2+2] cycloaddition of 1,6-enynes and alkynes was developed. Both internal and terminal alkynes were suitable substrates to access bicyclohexadienes with high yields in a single step. An intriguing ruthenium-catalyzed bicycloannulation of nitrogen-tethered 1,6-enynes has also been developed. For these cyclizations, only the electrophilic and alkynophilic ruthenium complex [RuCl2(CO)3]2 was able to perform the reaction. The exclusive formation of 3-azabicylo[4.1.0]hept-1-enes was observed with 1,6-enynes featuring an internal alkyne unit. These cyclization reactions fulfil the atom-economical reactions principle and are discussed on the basis of their mechanisms of formation.
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Rui Liu. Ruthenium (II) - catalysed enyne carbocyclization reactions. Organic chemistry. Ecole Centrale Marseille, 2017. English. ⟨NNT : 2017ECDM0004⟩. ⟨tel-02077564⟩

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