Interrogating Pd(II) Anion Metathesis Using a Bifunctional Chemical Probe: A Transmetalation Switch

Area of Science:

• Organometallic Chemistry
• Synthetic Organic Chemistry

Background:

• Ligand metathesis of palladium(II) complexes is crucial for cross-coupling reactions.
• Understanding and controlling these metathesis events is key to directing reaction pathways.

Purpose of the Study:

• To investigate halide→OH anion metathesis of palladium(II) complexes.
• To identify factors influencing metathesis and control cross-coupling pathways.
• To demonstrate synthetic utility in cascade reactions.

Main Methods:

• Utilized vinylBPin as a bifunctional chemical probe.
• Studied palladium(II)-dependent cross-coupling pathways.
• Analyzed variables impacting anion metathesis and transmetalation.

Main Results:

• Identified key variables controlling halide→OH anion metathesis.
• Demonstrated control over organoboron transmetalation, switching between Suzuki-Miyaura and Mizoroki-Heck pathways.
• Achieved selective synthesis of borylated and non-borylated carbocycles, including steroid-like structures, via cascade reactions.

Conclusions:

• Ligand metathesis provides a switch to control palladium-catalyzed cross-coupling outcomes.
• This strategy enables efficient synthesis of diverse carbocyclic scaffolds.