Room Temperature Anhydrous Suzuki-Miyaura Polymerization Enabled by C-S Bond Activation

Angew Chem Int Ed Engl. 2023 Oct 2;62(40):e202309922. doi: 10.1002/anie.202309922. Epub 2023 Aug 23.

Abstract

The Suzuki-Miyaura cross-coupling is one of the most important and powerful methods for constructing C-C bonds. However, the protodeboronation of arylboronic acids hinder the development of Suzuki-Miyaura coupling in the precise synthesis of conjugated polymers (CPs). Here, an anhydrous room temperature Suzuki-Miyaura cross-coupling reaction between (hetero)aryl boronic esters and aryl sulfides was explored, of which universality was exemplified by thirty small molecules and twelve CPs. Meanwhile, the mechanistic studies involving with capturing four coordinated borate intermediate revealed the direct transmetalation of boronic esters in the absence of H2 O suppressing the protodeboronation. Additionally, the room temperature reaction significantly reduced the homocoupling defects and enhanced the optoelectronic properties of the CPs. In all, this work provides a green protocol to synthesize alternating CPs.

Keywords: Conjugated Polymers; C−S Bond Activation; Protodeboronation; Room-Temperature Reactions; Suzuki-Miyaura Cross-Coupling.