Tetrachloromethane (CT) is transformed in biological systems via two major pathways: hydrogenolysis to trichloromethane (CF) and hydrolysis to carbon dioxide. The mechanism of hydrolysis is poorly understood. One possibility is a hydrolytic reduction of CT to formate or carbon monoxide followed by oxidation to carbon dioxide. In biological systems, formate and carbon monoxide are readily oxidiz...

Palladium-catalyzed cyclization of β-alkylthio dienone derivatives affords 2-cyclopentenones in a regio- and stereoselective manner in the presence of silane. C-S activation, intramolecular carbopalladation and hydrogenolysis construct the cascade process.

Ruthenium (Ru) supported on activated carbon (AC) and carbon nanotubes (CNTs) was carried out in the hydrogenolysis of sorbitol to ethylene glycol (EG) and 1,2-propanediol (1,2-PD) under the promotion of tungsten (WOx) species and different bases. Their catalytic activities and glycols selectivities strongly depended on the support properties and location of Ru on CNTs, owning to the altered me...

The reactivity of Fe(0) toward chlorinated ethylenes was examined utilizing a photochemically generated, highly reactive Fe(0) complex. Irradiation of (dmpe)2FeH2 (dmpe = Me2PCH2CH2PMe2) with 360 nm light generated a 16-e(-), Fe(0) intermediate that reacted to dechlorinate chlorinated ethylenes in a stepwise fashion, consistent with a hydrogenolysis dechlorination pathway. The source of the hyd...

Mechanistic studies of the hydrogenolysis of aryl ethers by nickel were undertaken with (diphosphine)aryl methyl ethers. A Ni(0) complex containing Ni-arene interactions adjacent to the aryl-O bond was isolated. Heating led to aryl-O bond activation and generation of a nickel aryl methoxide complex. Formal β-H elimination from this species produced a nickel aryl hydride which can undergo reduct...

Several reactions representing important categories of catalytic systems have been studied on chemically modified single crystal surfaces. These reactions are methanation of CO and CO:. hydrogenolysis of ethane. hydrogenation of ethylene. and q&propane ring-opening and hydrogenolysis. Poisoning of the above reactions by ordered. suhmonolayer coverages of sulfur shou large nonlinear effects for ...

The efficiency and stereoselectivity of the conjugate addition of lithium (Z)- or (E)-beta-amino ester enolates, generated by lithium amide conjugate addition to an alpha,beta-unsaturated ester or deprotonation of a beta-amino ester, respectively, to a range of alpha,beta-unsaturated acceptors has been investigated. Deprotonation of a beta-amino ester with LDA, followed by conjugate addition to...