B2Pin2-Enabled Reductive Thioesterification of Aryl Triflates with Thiocarbonates

In this work, we demonstrate aryl thioester synthesis via an unprecedented B2Pin2-mediated reductive coupling of aryl triflates with thiocarbonates. This method demonstrates good to high efficiency for 2,6-disubstituted aryl substrates, which are thought to be challenging due to high steric hinderance. The practicality of this method was showcased by rapid thioesterification of triflates derived from pharmaceutical compounds such as Apixaban, Ezetimibe, and Ethinyl estradiol. This work may further invoke development of B2Pin2-mediated reductive C(sp2)-C(sp2) coupling under earth-abundant transition metal catalysis, avoiding otherwise use of Zn and Mn, which may present scalability and metal residue issues.