The tenth anniversary of Suzuki polycondensation (SPC)

Abstract

This article describes the successful transfer of the Suzuki cross-coupling (SCC) reaction to polymer synthesis, one of the major developments within the last decade of polymer synthesis. The polymers prepared by Suzuki polycondensation (SPC) and its Ni-catalyzed reductive counterpart are soluble and processable poly(arylene)s that, because of their rigid and conjugated backbones, are of interest for the materials sciences. Achievable molar masses easily compete with those of traditional polyesters and polyamides. This article also provides insight into some synthetic problems associated with the transfer of SCC from low molar mass organic chemistry to high molar mass polymer chemistry by addressing issues such as monomer purity, stoichiometric balance, achievable molar masses, and defects in the polymer structure. Although the emphasis of this article is synthetic and structural issues, some potential applications of the polyarylenes obtained are briefly mentioned. Together with the enormous developments in the areas of metallocene, ring-opening metathesis, and acyclic diene metathesis polymerization, the success of SPC impressingly underlines the increasing importance of transition-metal-catalyzed CC-bondforming reactions in polymer synthesis.

Synthesis and Orientation of Fluorene Containing Reactive Mesogens

“…In the course of our studies we found that the use of free hydroxy groups in Suzuki-cross-coupling reactions leads to the formation of undesirable side products. [24] For that reason the OH-group of the 2-bromofluorene 6 was protected with tetrahydropyran (THP). [25] After the Suzuki-cross-coupling the THP group is cleaved quantitatively with a small amount of HCl.…”

Catalytic Polymerization and Post Polymerization Catalysis Fifty Years After the Discovery of Ziegler's Catalysts

“…[243] The prospects of the Suzuki coupling was reviewed by Schlüter on occasion of its 10 th anniversary. [244] The formation of polyarylenes proceeds via the repeated sequences of oxidative addition of aryl halides, boronic acids, or triflates on palladium(0) and formation of palladium(II) biaryl complexes followed by reductive elimination, carbon-carbon crosscoupling, and recovery of palladium(0). The catalytic cycle of polyarylenevinylene formation involves the repeated reaction sequences of oxidative addition followed olefin insertion, b-hydride elimination, and HX abstraction in the presence of a base to regain palladium(0).…”

Optical, Electrochemical, Magnetic, and Conductive Properties of New Poly(indolocarbazole‐alt‐bithiophene)s

“…The polymer syntheses are carried out using either Stille [29] or Suzuki [30] coupling reaction (Scheme 2). The BT copolymers P2ICTT and P3ICTT are synthesized using 5,5 0 -ditrimethylstannyl-2,2 0 -bithiophene [31,32] and compounds 3 or 4 in THF with a catalytic amount of Pd(PPh 3 ) 4 .…”

“…Moreover, thiophene units should have some good impact over the molecular organization as found with copolymers based on fluorene and indenofluorene. [28] For all these reasons, we report the synthesis of 2,8-and 3,9-poly(indolocarbazole-alt-bithiophene)s using either Stille [29] or Suzuki [30] coupling. Moderate electrondonating unit, bithiophene (BT), and strong electrondonating unit, bis(3,4-ethylenedioxythiophene) (BiEDOT), have been incorporated to the polymeric structures.…”