The [Ni(IMes)2]-catalyzed transformation of fluoroarenes into arylboronic acid pinacol esters via C-F bond activation and transmetalation with bis(pinacolato)diboron (B2pin2) is reported. Various partially fluorinated arenes with different degrees of fluorination were converted into their corresponding boronate esters.
An efficient Suzuki-Miyaura cross-coupling reaction of perfluorinated arenes with aryl boronate esters using NHC nickel complexes as catalysts is described. The efficiencies of different boronate esters (p-tolyl-Beg, p-tolyl-Bneop, p-tolyl-Bpin, p-tolyl-Bcat) and the corresponding boronic acid (p-tolyl-B(OH)2) in this type of cross-coupling reaction were evaluated (eg, ethyleneglycolato; neop, neopentylglycolato; pin, pinacolato; cat, catecholato). Aryl-Beg was shown to be the most reactive boronate ester among those studied. The use of CsF as an additive is essential for an efficient reaction of hexafluorobenzene with aryl neopentylglycolboronates.
Ringerweiterung von NHCs! Die Reaktion N‐heterocyclischer Carbene (NHCs) mit Hydrosilanen Ph4−nSiHn (n=1, 2, 3) führt zu einem vollständigen Aufbrechen des Heterocyclus unter Silyleninsertion in eine der C‐N‐Bindungen des Carbens (siehe Schema; R=Alkyl, Aryl).
In this detailed study we report on the structures of the widely employed diboron(4) compounds bis(pinacolato)diboron (Bpin) and bis(neopentyl glycolato)diboron (Bneop), as well as bis(ethylene glycolato)diboron (Beg) and tetrakis(dimethylamino)diboron (B(NMe)), and their reactivity, along with that of bis(catecholato)diboron (Bcat) with backbone saturated and backbone unsaturared N-heterocyclic carbenes (NHCs) of different steric demand. Depending on the nature of the diboron(4) compound and the NHC used, Lewis-acid/Lewis-base adducts or NHC ring-expansion products stemming from B-B and C-N bond activation have been observed. The corresponding NHC adducts and NHC ring-expanded products were isolated and characterised via solid-state and solution NMR spectroscopy and X-ray diffraction. In general, we observed B-B bond and C-N bond activation at low temperature for Beg, at room temperature for Bneop and at higher temperature for Bcat. The reactivity strongly depends on steric effects of the NHCs and the diboron(4) compounds, as well as on the corresponding Lewis-basicity and Lewis-acidity. Our results provide profound insight into the chemistry of these diboron(4) reagents with the nowadays ubiquitous NHCs, the stability of the corresponding NHC adducts and on B-B bond activation using Lewis-bases in general. We demonstrate that B-B bond activation may be triggered even at temperatures as low as -40 °C to -30 °C without any metal species involved. For example, the reactions of Beg with sterically less demanding NHCs such as MeIm and iPrIm in solution led to the corresponding ring-expanded products at low temperatures. Furthermore, boronium [LB(OR)] and borenium [LB(OR)] cations have been observed from the reaction of the bis-borate Beg with the NHCs iPrIm and MeIm, which led to the conclusion that the activation of bis-borates with NHCs (or Lewis-bases in general) might be a facile and simple route to access such species.
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