938083-09-1Relevant articles and documents
Toward functional carboxylate-bridged diiron protein mimics: Achieving structural stability and conformational flexibility using a macrocylic ligand framework
Do, Loi H.,Lippard, Stephen J.
, p. 10568 - 10581 (2011)
A dinucleating macrocycle, H2PIM, containing phenoxylimine metal-binding units has been prepared. Reaction of H2PIM with [Fe2(Mes)4] (Mes = 2,4,6-trimethylphenyl) and sterically hindered carboxylic acids, Phsub
Antimony(v) cations for the selective catalytic transformation of aldehydes into symmetric ethers, α,β-unsaturated aldehydes, and 1,3,5-trioxanes
Arias Ugarte, Renzo,Devarajan, Deepa,Mushinski, Ryan M.,Hudnall, Todd W.
supporting information, p. 11150 - 11161 (2016/07/20)
1-Diphenylphosphinonaphthyl-8-triphenylstibonium triflate ([2][OTf]) was prepared in excellent yield by treating 1-lithio-8-diphenylphosphinonaphthalene with dibromotriphenylstiborane followed by halide abstraction with AgOTf. This antimony(v) cation was found to be stable toward oxygen and water, and exhibited exceptional Lewis acidity. The Lewis acidity of [2][OTf] was exploited in the catalytic reductive coupling of a variety of aldehydes into symmetric ethers of type L in good to excellent yields under mild conditions using Et3SiH as the reductant. Additionally, [2][OTf] was found to selectively catalyze the Aldol condensation reaction to afford α-β unsaturated aldehydes (M) when aldehydes with 2 α-hydrogen atoms were used. Finally, [2][OTf] catalyzed the cyclotrimerization of aliphatic and aromatic aldehydes to afford the industrially-useful 1,3,5 trioxanes (N) in good yields, and with great selectivity. This phosphine-stibonium motif represents one of the first catalytic systems of its kind that is able to catalyze these reactions with aldehydes in a controlled, efficient manner. The mechanism of these processes has been explored both experimentally and theoretically. In all cases the Lewis acidic nature of the antimony(v) cation was found to promote these reactions.
19F NMR study of ligand dynamics in carboxylate-bridged dIIron(II) complexes supported by a macrocyclic ligand
Minier, Mikael A.,Lippard, Stephen J.
, p. 18111 - 18121 (2015/10/28)
A series of asymmetrically carboxylate-bridged diiron(ii) complexes featuring fluorine atoms as NMR spectroscopic probes, [Fe2(PIM)(Ar4F-PhCO2)2] (10), [Fe2(F2PIM)(ArTolCO2
Triflic acid catalyzed reductive coupling reactions of carbonyl compounds with O-, S-, and N-nucleophiles
Gellert, Beate A.,Kahlcke, Nils,Feurer, Markus,Roth, Stefanie
supporting information; experimental part, p. 12203 - 12209 (2011/11/07)
Highly efficient metal-free reductive coupling reactions of aldehydes and ketones with a range of nucleophiles in the presence of triflic acid (1-5 mol %) as the catalyst are presented. The reactions can be performed at ambient temperature without exclusion of moisture or air. A range of symmetrical and unsymmetrical ethers were obtained by this method in high yields and short reaction times. For the first time, the influence of additional functionalization has been studied. Furthermore, the formation of thioethers from ketones (by addition of unmodified thiols) and of sulfonamides from either aldehydes or ketones has been achieved under catalytic conditions.
