Novel Substrates for Palladium‐Catalyzed Coupling Reactions of Arenes

Abstract

Arenes and heteroarenes are ubiquitous substructures in biologically active agents and new materials. Thus, functionalization ("refinement") of simple arene precursors is still of major importance for preparative organic chemistry. During the last 20 years, especially transition-metal-catalyzed cross-coupling reactions of aryl halides and triflates have given arene chemistry new impetus. The first industrial applications were realized a few years ago. Quite recently, carbonic acid derivatives such as anhydrides and esters have added to the scope of substrates for these coupling reactions. Some recent developments in this area are presented in this Minireview.

Recent Advances in Acyl Suzuki Cross-Coupling

“…Acyl Suzuki cross-coupling involves the coupling of an organoboron reagent with an acyl electrophile (acyl halide, anhydride, ester, amide) ( Figure 1B), and in parallel to the biaryl counterpart typically proceeds by a C(acyl)-C(sp 2 ) disconnection [6,7]. Since its first discovery in 1999, acylative Suzuki cross-coupling has been established as a new and useful technique for the synthesis of ketones as a catalytic alternative to stoichiometric nucleophilic additions of organometallic reagents or Friedel-Crafts reactions of acyl electrophiles [8][9][10][11].…”

Beyond TPPTS: New Approaches to the Development of Efficient Palladium‐Catalyzed Aqueous‐Phase Cross‐Coupling Reactions

“…Researchers continue to seek catalysts and reaction conditions that will provide high catalyst turnover numbers (TON) and frequencies (TOF) in an effort to reduce the amount of catalyst required for a given reaction. Over the past decade there has been a growing effort to widen the scope of organic electrophiles that can be used under mild conditions to include aryl chlorides,30 aryl tosylates,31–33 benzoic acid derivatives,34 and aliphatic halides 35…”

Supported Palladium Catalysts in Heck Coupling Reactions - Problems,Potential and Recent Advances

“…In the following years, many efforts have been made to extend the scope of the Heck reaction. Various classes of compounds, such as aryl triflates [18], aromatic anhydrides [19,20] and carboxylic acids [21,22], aryl diazonium salts (Matsuda-Heck reaction) [23,24], benzyl halides [25,26], halides of benzoic acids (Blaser-Heck reaction) [27][28][29], alkyl halides [30] and boronic acids [31,32] have been utilized besides aryl halides, which still play an outstanding role.…”