NEST
Volume design and example of complex A'. Credit: JACS Au (2023). DOI: 10.1021/jacsau.3c00159
Remarkable
strides in the field of enantioselective catalysis have been made by
investigating the unique properties of pyrrolidinyl gold(I) complexes.
Researchers from the Prof. Echavarren
group at the Institute of Chemical Research of Catalonia (ICIQ-CERCA) in
collaboration with Dr. Maria Besora from the URV in Tarragona have published in JACS Au their pioneering study,
employing a combination of Density Functional Theory (DFT) calculations and the
newly developed NEST App.
The findings pave the way for enhanced
understanding of electronic and steric effects and expedite the design of novel
chiral ligands for enantioselective reactions.
Building upon the success of their
previous work with chiral gold(I) catalysts, the research team focused on exploring
the impact of structural modifications on electronic and steric effects of the
ligands. To this end, they synthesized more than 20 new gold(I) complexes and
evaluated their performance in two key reactions: the enantioselective formal
[4+2] cycloaddition of arylalkynes with alkenes and the atroposelective
synthesis of 2-arylindoles through the cyclization of sulfonamidyl
diarylacetylenes.
Remarkably, the novel catalysts exhibited excellent enantioselectivities, highlighting the potential of the pyrrolidinyl gold(I) complex scaffold.
NEST tool. Credit: ICIQ
The
computational work carried out by Dr. Imma Escofet, in the group of Prof.
Echavarren, in collaboration with Dr. Besora was crucial for developing a
cutting-edge open-source tool called NEST App. This innovative software
computes the volume occupied by the atoms of a molecule within a defined
capsule-shaped region, enabling the detailed investigation of steric effects
within the binding pockets of gold(I) catalysts.
The data
generated by the NEST App provided valuable insights and facilitated the
prediction of experimental enantioselectivities, exhibiting reasonable
agreement with the actual experimental results. This new tool accelerates the
process of designing new chiral ligands, significantly reducing the time
required for optimization.
The study conducted by the team in Tarragona not only advances our fundamental understanding of enantioselective catalysis with pyrrolidinyl gold(I) complexes but also establishes a powerful platform for the future development of highly efficient and selective catalysts. These findings hold tremendous potential for revolutionizing the field and driving transformative advancements in the synthesis of complex chiral molecules.
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