Tracking electron motion driving the Suzuki-Miyaura cross-coupling reaction

Area of Science:

• Organic Chemistry
• Computational Chemistry
• Reaction Mechanisms

Background:

• The Suzuki-Miyaura cross-coupling is a vital reaction in organic synthesis.
• Understanding the electron dynamics during transmetalation is crucial for reaction optimization.

Purpose of the Study:

• To elucidate the electron motion driving the transmetalation step in Suzuki-Miyaura cross-coupling.
• To compare the mechanistic pathways of boronate and oxo-palladium mechanisms using ROET.

Main Methods:

• Computational investigation using intrinsic reaction coordinate (IRC) calculations.
• Analysis of electron motion via reactive orbital energy theory (ROET).

Main Results:

• The boronate mechanism exhibits a lower activation barrier and a simpler reaction pathway compared to the oxo-palladium mechanism.
• ROET analysis demonstrated electron motion patterns consistent with experimental observations.
• The electronic roles of organoboronic acid and ancillary ligands were clarified by ROET.

Conclusions:

• ROET offers a novel perspective for understanding electron motion in metal-catalyzed reactions.
• The findings support the boronate mechanism as the predominant pathway in this Suzuki-Miyaura coupling.
• ROET provides valuable insights into the fundamental electronic processes governing catalytic reactions.