100004-77-1Relevant articles and documents
Copper-catalyzed fluorination of 2-pyridyl aryl bromides
Mu, Xin,Zhang, Hao,Chen, Pinhong,Liu, Guosheng
, p. 275 - 280 (2013)
Copper(i)-catalyzed cross-coupling of aryl halides is the subject of extensive interest in synthetic chemistry, but the related catalytic fluorination is unsuccessful. Herein, we have developed a novel copper-catalyzed fluorination of aryl bromides using AgF as the fluorine source. In this transformation a pyridyl directing group is essential for successful catalytic fluorination. A XANES/EXAFS study indicated that the presence of the pyridyl group is essential to stabilize the Cu(i) species and accelerate oxidative addition of the aryl bromide. Further mechanistic studies implicated a Cu(i/iii) catalytic cycle in this Cu(i)-catalyzed fluorination, and final aryl C-F bond formation possibly proceeds through an irreversible reductive elimination of the ArCu(iii)-F species. This rare report of catalytic fluorination by a copper catalyst provides a valuable foundation for further development of Cu(i)-catalyzed fluorination of aryl halides.
Synthesis of Chemically and Configurationally Stable Monofluoro Acylboronates: Effect of Ligand Structure on their Formation, Properties, and Reactivities
Noda, Hidetoshi,Bode, Jeffrey W.
supporting information, p. 3958 - 3966 (2015/04/14)
The recent disclosures of two classes of acylborons, potassium acyltrifluoroborates (KATs) and N-methyliminodiacetyl (MIDA) acylboronates, demonstrated that certain acylboron species can be both remarkably stable and uniquely reactive. Here we report new classes of ligands for acylboronates that have a significant influence on the formation, properties, and reactivities of acylboronates. Our systematic investigations identified a class of neutral, monofluoroboronates that can be prepared in a one step, gram-scale fashion from readily accessible KATs. These monofluoroboronates are stable to air, moisture, and silica gel chromatography and can be easily handled without any special precautions. X-ray crystallography, NMR spectroscopy, and HPLC studies showed that they are tetravalent, configurationally stable B-chiral acylboronates. Significantly, the ligands on the boronate allow for fine-tuning of the properties and reactivity of acylboronates. In amide-forming ligation with hydroxylamines under aqueous conditions, a considerable difference in reactivity was observed as a function of ligand structure. The solid-state structures suggested that subtle steric and conformational factors modulate the reactivities of the acylboronates.
Synthesis in 3 Azafluorene Group. Part-III
Chatterjea, J. N.,Shaw, S. C.,Prasad, Y.,Singh, R. P.
, p. 1028 - 1031 (2007/10/02)
The Hey-Elks route to arylated pyridines has been utilised in the synthesis of 3-azafluorenes.The pyrido-coumarin (23) and the related chromene (24) have been synthesised.