Simple catalysts formed in situ from iron chloride and a wide range of monodentate and bidentate phosphines and arsines have been screened in the coupling of alkyl halides bearing beta-hydrogens with aryl Grignard reagents. The best of these show excellent activity, as do catalysts formed in situ with monodentate trialkyl and triaryl phosphite ligands. N-heterocyclic carbene-based precatalysts, either preformed or made in situ, also show excellent performance.
N-H carbazoles can be produced from 2-chloroanilines and aryl bromides via consecutive catalytic amination and C-H activation. In many instances, this can be done in a tandem manner in one pot. The methodologies developed can be used in the synthesis of a range of carbazoles, including the natural products Clausine P and glycozolidine and a precursor in the synthesis of Clausines H, K, O, and 7-methoxy-O-methylmukonal, and can be extended to the synthesis of indoles.
Iron nanoparticles, either formed in situ stabilized by 1,6-bis(diphenylphosphino)hexane or polyethylene glycol (PEG), or preformed stabilized by PEG, are excellent catalysts for the cross-coupling of aryl Grignard reagents with primary and secondary alkyl halides bearing beta-hydrogens and they also prove effective in a tandem cyclization/cross-coupling reaction.
The synthesis of a range of chiral palladium bis(phosphite) pincer complexes has been achieved via C-H activation of the parent ligands and one of the complexes formed shows good activity in the catalytic allylation of aldehydes.
Simple chlorodiisopropylphosphine adducts of rhodium, either pre-formed or formed in situ, prove to be highly effective catalysts for the ortho-arylation of phenols.
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