- Iron-Catalyzed Ortho C-H Methylation of Aromatics Bearing a Simple Carbonyl Group with Methylaluminum and Tridentate Phosphine Ligand
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Iron-catalyzed C-H functionalization of aromatics has attracted widespread attention from chemists in recent years, while the requirement of an elaborate directing group on the substrate has so far hampered the use of simple aromatic carbonyl compounds such as benzoic acid and ketones, much reducing its synthetic utility. We describe here a combination of a mildly reactive methylaluminum reagent and a new tridentate phosphine ligand for metal catalysis, 4-(bis(2-(diphenylphosphanyl)phenyl)phosphanyl)-N,N-dimethylaniline (Me2N-TP), that allows us to convert an ortho C-H bond to a C-CH3 bond in aromatics and heteroaromatics bearing simple carbonyl groups under mild oxidative conditions. The reaction is powerful enough to methylate all four ortho C-H bonds in benzophenone. The reaction tolerates a variety of functional groups, such as boronic ester, halide, sulfide, heterocycles, and enolizable ketones.
- Shang, Rui,Ilies, Laurean,Nakamura, Eiichi
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supporting information
p. 10132 - 10135
(2016/08/31)
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- PHOTOOXYGENATIONS PAR TRANSFERT D'ELECTRON SENSIBILISEES PAR LE DICYANO-9,10 ANTHRACENE. ROLE DU SOLVANT ET FORMATION D'OXYGENE SINGULET.
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Photooxygenation of naphtalenic compounds sensitized by electron acceptors like 9,10 dicyanoanthracene (DCA) is shown to proceed by two distinct ways depending on the solvent polarity.In a polar solvent superoxide ion (O2-.) as well as singlet oxygen (1O2*) are involved while in a non polar solvent only singlet oxygen is produced.
- Santamaria, J.,Gabillet, P.,Bokobza, L.
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p. 2139 - 2142
(2007/10/02)
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