posted on 2024-01-12, 17:08authored byAsaf Hassin, Romy Levy, Natalia Fridman, Mark Gandelman
Catalytic stereoselective synthesis of substituted 1,3-dienes
represents
an important facet of modern synthetic chemistry. In this study, we
introduce novel ruthenium complexes with triazole-based phosphine
ligands, demonstrating their high catalytic activity in synthesizing
(1E,3E)-1,4-disubstituted-1,3-dienyl
esters from aryl acetylenes and carboxylic acids. Our research unveils
the cooperative role of the Ru–triazole complexes, elucidating
that the internal basicity of the triazole unit likely plays a role
in the activation of carboxylic acids. Various alkynes and carboxylic
acids featuring diverse stereoelectronic substituents were found to
be compatible with our synthetic protocol. Our work offers an alternative
mechanistic pathway for stereodefined product formation, avoiding
the formation of Ru–biscarbene intermediates observed in related
catalytic systems.