Efficient One‐Pot Cross‐Coupling of Two Aryl Halides by Stannylation/Stille Reaction in Water under Microwave Irradiation

Abstract

A simple and highly efficient one‐pot approach has been developed for the Pd(PPh3)4‐catalyzed cross‐coupling of two different aryl or heteroaryl bromides/iodides. This method involves the combined use of microwave irradiation and water as a single solvent to achieve sequential stannylation and Stille cross‐coupling reactions, which allows rapid access to a wide variety of biaryls in good to high yields. Furthermore, utilizing this step‐economical protocol, 2,5‐dibromopyridine was iteratively diarylated and the Boscalid intermediate was also synthesized in a one‐pot manner.

Stannylation of Aryl Halides, Stille Cross‐Coupling, and One‐Pot, Two‐Step Stannylation/Stille Cross‐Coupling Reactions under Solvent‐Free Conditions

“…This synthetic sequence has toxicity issues, environmental concerns, and low efficiency in terms of step economy. Thus, the development of one‐pot, two‐step stannylation, followed by Stille cross‐coupling (SSC), recently reported by Xin Hong Duan et al, is very attractive . Palladium‐mediated SSC was performed in water under microwave irradiation.…”

Microwave-Assisted Palladium-Catalyzed Cross-Coupling Reactions: Generation of Carbon–Carbon Bond

“…Moderate to excellent yields were achieved in the presence of various functional groups such as: F, Ac, CHO, CF3, CN, CO2Et, CO2H, OH, OMe, and NO2 under microwave heating in water at 100 °C (Scheme 37). Although the one-pot approach comprises the elimination of the isolation/purification steps of the aryl stannanes, it should bypass the production of undesirable homocoupling resulting from stannylation reaction [92]. Van der Eycken and coworkers have described that Stille coupling reactions of few substrates were efficiently proceeded under microwave irradiation in moderate yields using Pd(PPh3)4, rather than under conventional heating condition.…”

“…Moderate to excellent yields were achieved in the presence of various functional groups such as: F, Ac, CHO, CF 3 , CN, CO 2 Et, CO 2 H, OH, OMe, and NO 2 under microwave heating in water at 100 • C (Scheme 37). Although the one-pot approach comprises the elimination of the isolation/purification steps of the aryl stannanes, it should bypass the production of undesirable homocoupling resulting from stannylation reaction[92].Catalysts 2020, 10, x FOR PEERREVIEW 19 of Palladium-catalyzed one-pot hydrostannylation/Stille coupling reactions.…”

Reactivity of Polar Organometallic Compounds in Unconventional Reaction Media: Challenges and Opportunities

“…A simple and efficient one‐pot methodology using water as the solvent has been developed by Duan and co‐workers; with Pd(PPh 3 ) 4 as a catalyst, effective cross‐coupling of a variety of aryl and heteroaryl bromides/iodides could be accomplished 120. This method requires the use of microwave irradiation and involves sequential stannylation followed by a Stille cross‐coupling process, as depicted in Scheme for the synthesis of 73 .…”