Copper-catalysed cross-couplings of arylboronate esters with aryl and heteroaryl iodides and bromides

Abstract

Cu-catalysed cross-coupling for mono- and di-arylations of aryl and heteroaryl iodides and bromides is achieved with arylboronate esters.

Insight into Transmetalation Enables Cobalt-Catalyzed Suzuki–Miyaura Cross Coupling

“…These practical motivations, coupled with opportunities for new modes of reactivity and potential expansion of reaction scope, have prompted exploration of Earth abundant, first row transition metals as potential catalysts for the Suzuki–Miyaura reaction. Considerable progress has been made with nickel- − and copper- − catalyzed variants, but reactivity with earlier first row transition metals such as iron and cobalt has remained elusive. State-of-the-art iron- − and cobalt- − catalyzed C–C cross coupling methods rely on more reactive nucleophiles rather than the preferable neutral boron reagents associated with Suzuki–Miyaura chemistry (Scheme ).…”

Fluorinated Aryl Boronates as Building Blocks in Organic Synthesis

“…As described in sections 4.3.1–4.3.3, the palladium‐catalyzed Suzuki‐Miyaura cross‐coupling of fluorinated aryl boronic acids requires one of the following methods to achieve acceptable to good yield: (i) a stoichiometric amount of silver oxide; (ii) a highly reactive palladium precatalyst such as second, third, and fourth generation Buchwald precatalysts or Carrow precatalysts; (iii) a one pot‐two step iridium‐catalyzed C−H borylation of fluoroarenes with B 2 pin 2 followed by a palladium‐catalyzed Suzuki‐Miyaura cross‐coupling reaction; or (iv) via protection of the boron using more stable moieties such as Bdan ( vide supra ). Several reports employing economically‐viable and earth‐abundant low toxicity metals, such as copper, as catalyst systems have been of recent significant interest for Suzuki‐Miyaura cross‐coupling reactions [142–149] . Thus, Radius and Marder reported the copper‐catalyzed Suzuki‐Miyaura cross‐coupling of highly fluorinated aryl boronic esters with aryl halides [17] .…”

Synthesis of symmetrical terphenyl derivatives by PdCl2-catalyzed Suzuki–Miyaura reaction of dibromobenzene using 3-(diphenylphosphino)propanoic acid as a ligand

“…3,3'',4,4'',5,5''-hexafluoro-1,1':4',1''-terphenyl (3f) [5] White solid, Isolated yield = 76 %; mp 102.2-102.8 ºC; 1 H NMR (400 MHz, CDCl 3 ): δ (ppm) 7.59 (s, 4H), 7.23 (dd, J = 14.1, 6.4 Hz, 4H).…”