Rhenium Alkyne Catalysis: Sterics Control the Reactivity

Metathesis reactions, including alkane, alkene, and alkyne
metatheses,
have their origins in the fundamental understanding of chemical reactions
and the development of specialized catalysts. These reactions stand
as transformative pillars in organic chemistry, providing efficient
rearrangement of carbon–carbon bonds and enabling synthetic
access to diverse and complex compounds. Their impact spans industries
such as petrochemicals, pharmaceuticals, and materials science. In
this work, we present a detailed mechanistic study of the Re(V) catalyzed
alkyne metathesis through density functional theory calculations.
Our findings are in agreement with the experimental evidence from
Jia and co-workers and unveil critical factors governing catalyst
performance. Our work not only enhances our understanding of alkyne
metathesis but also contributes to the broader landscape of catalytic
processes, facilitating the design of more efficient and selective
transformations in organic synthesis.