Ruiting Liu

FeCl3·6H2O Catalyzed Disproportionation of Allylic Alcohols and Selective Allylic Reduction of Allylic Alcohols and Their Derivatives with Benzyl Alcohol

Iron chloride has been found to be an efficient catalyst for the disproportionation of allylic alcohols, which provides a convenient method for selective transformation of allylic alcohols to alkenes and alpha,beta-unsaturated ketones. Furthermore, this catalytic system is also effective for highly selective allylic reduction of allylic alcohols, allylic ethers, and allylic acetates with benzyl alcohol under neutral and convenient reaction conditions.

Controllable one-step synthesis of spirocycles, polycycles, and di- and tetrahydronaphthalenes from aryl-substituted propargylic alcohols.

A novel, convenient, and efficient method has been developed for selective synthesis of spirocycle, polycycle, and di- and tetrahydronaphthalene systems from aryl-substituted propargylic alcohols by FeCl3- or TsOH-catalyzed multiple activations of unsaturated C-C bonds and C-H bonds.

A New Strategy for Ring Modification of Metallocenes: Carbodiimide Insertion into the η5-Y−C5H5 Bond and Subsequent Isomerization

Unusual insertion of carbodiimide into the Y-Cp (Cp = C(5)H(5)) bond and isomerization of the resulting cyclopentadienyl (Cp)-substituted amidinate complex to the amidino-substituted Cp complex have been established, representing an efficient and simple method for ring modification of sensitive metallocenes. All products, including the rare four-center interaction precursor of the insertion, have been characterized by X-ray structural analyses.

FeCl 3 ·6H 2 O-catalyzed selective reduction of allylic halides to alkenes with concomitant oxidation of benzylic alcohols to aldehydes

Iron-catalyzed direct reduction of allylic halides with benzylic alcohol was achieved, providing a new, simple, and efficient method for conducting highly regioselective hydrodehalogenation. This method not only features a readily available reductant, an inexpensive catalyst, simple manipulation, and good tolerance of functional groups including nitriles, nitro, esters, and methoxyl groups, it also has mild reaction conditions and shows complete regioselectivity in that only halides sited at the allylic position are reduced. Alternatively, this method can be applied in the selective transformation of benzylic alcohols to aromatic aldehydes without overoxidation to carboxylic acids.

Syntheses, Cycloaminocarbonylation and Amidination of Rare Earth o -Aminobenzamido Dianion Complexes Bearing Cyclopentadienyl Co-ligand

Treatment of Cp 3 Ln with o -aminobenzamide followed by crystallization in a HMPA and toluene mixture affords the tetranuclear organolanthanide complexes [CpLn( μ - η 2 : η 2 -NHC 6 H 4 CONH)( μ 3 - η 1 : η 1 : η 2 -NHC 6 H 4 CONH)LnCp(HMPA)} 2 (Ln=Yb, 1a ; Er, 1b ; Y, 1c ). Reaction of 1 with PhNCO ( n PhNCO / n 1 =4) in toluene gives the dianionic quinazolyldiolate (Quo) complexes [Cp 2 Ln( μ 3 - η 2 : η 2 : η 1 -Quo)] 3 Ln(HMPA) 2 (Ln=Yb, 2a ; Er, 2b ; Y, 2c ), indicating that one isocyanate molecule can undergo the tandem reaction with both NH and CONH of 1 to construct a quinazoly-ldiolate skeleton, companying with the elimination of PhNH 2 . However, 1a ~ 1c react with i PrN=C=N i Pr under the same conditions to give only the single ArNH addition products {Cp 2 Ln[ μ - η 1 : η 1 : η 2 - i PrNC(NH i Pr)NC 6 H 4 CONH]} 3 Ln(HMPA) 3 (Ln=Yb, 3a ; Er, 3b ; Y, 3c ). Furthermore, treatment of Cp 3 Ln with o -aminobenzamide followed by reacting with i PrN=C=N i Pr gave {CpLn[ μ - η 1 : η 2 : η 2 -NHCOC 6 H 4 NC(NH i Pr)N i Pr]} 2 (Ln=Yb, 4a ; Er, 4b ; Y, 4c ). Noticeably, HMPA could induce the transformation of 4 into 3 by a ligand redistribution.