Abstract
<jats:title>Abstract</jats:title> <jats:p>This chapter presents step by step procedure for anhydrous, homogeneous, Suzuki‐Miyaura cross‐coupling of boronic esters using potassium trimethylsilanolate. The Suzuki‐Miyaura reaction is significantly exothermic, and appropriate care should be taken. A cross‐coupling method that could harness the differential reactivity of boronic esters would provide researchers an additional point of optimization in the Suzuki‐Miyaura reaction. Such a method would ideally be anhydrous, to preclude ester hydrolysis and protodeboronation. By exchanging the boronic acid for the cis‐2,3‐ tetrahydrofurandiol or neopentyl glycol ester, and by using TMSOK as the base in ethereal solvents, the reaction time could be decreased 10‐fold. The improvements in rate and yield are attributed entirely to the use of boronic esters in concert with TMSOK. The use of TMSOK as a soluble base allows for a homogeneous, anhydrous Suzuki‐Miyaura cross coupling that improves reproducibility and enables the cross‐coupling of fast‐acting boronic esters.</jats:p>