Palladium-catalyzed carbene coupling polymerization: synthesis of E-poly(arylene vinylene)s

Abstract

The Pd-catalyzed carbene coupling reaction of N-tosylhydrazones and benzyl bromides has been developed into a polymerization process for the first time, providing an efficient method for the synthesis of poly(arylene...

Who is Who in the Carbene Chemistry of N‐Sulfonyl Hydrazones

“…This polymerization process is also used to introduce the CF 3 group to each vinylene carbon atom in the polymer main chain (Scheme 11b). [ 95 ]…”

Synthesis of Poly(arylenevinylene)s by Rhodium-Catalyzed Stitching Polymerization/Alkene Isomerization

“…π-Conjugated polymers have been actively investigated as potentially useful materials for optoelectronic devices such as organic light-emitting diodes and organic photovoltaics . Among them, poly­(arylenevinylene)­s constitute an important class of such polymers, ,,, and one of the dominant factors to determine their properties is the structure of their repeating units, which have led to the development of various repeating unit structures to date. ,,, Regarding the synthetic methods of poly­(arylenevinylene)­s, , in addition to the classical approaches such as the Gilch route (Scheme a) and the Wessling route (Scheme b), transition-metal-catalyzed processes such as olefin metathesis polymerization (Scheme c) and palladium-catalyzed cross-coupling polymerization (Scheme d) have also been widely explored. However, all these existing methods toward poly­(arylenevinylene)­s require the use of monomers having corresponding aromatic structures that appear in the repeating unit, and the preparation of monomers can be tedious and difficult for the synthesis of poly­(arylenevinylene)­s having a complex aromatic structure.…”

Palladium hydrazonato complexes and their role in the Pd-catalyzed cross-coupling reactions of hydrazones as carbene precursors

“…The possibility of forming two new bonds on the carbene carbon has led to the discovery of interesting multicomponent cascade processes that allow the introduction of several functionalities in one synthetic step (Scheme 1). 1–3 The non-stabilized carbene fragments used in these reactions, usually CRR′ (R, R′ = H, hydrocarbyl), are generally transferred from a diazoalkane to palladium. Scheme 2 shows a general mechanism for these transformations that involves the formation of a Pd–R moiety, the carbene transfer to the metal, and a carbene migratory insertion step leading to a new C–C bond.…”