Abstract: For methane activation, various sulfonation systems using SO3 or H2SO4 have been well studied, however, sulfur dioxide (SO2), a preliminary source of SO3 and H2SO4, has not been used successfully. Herein, we report a novel methane sulfonation method to produce methanesulfonic acid (MSA) utilizing sulfur dioxide by a free radical mechanism. In the presence of H2O2 as a radical initiator, the reaction of SO2 and O2 in trifluoroacetic acid (TFAOH) furnished trifluoroacetylsulfuric acid (TFAOSO3H), which served as the radical propagator to facilitate H-abstraction of methane at low temperatures. In typical reactions, sulfur dioxide was incorporated into MSA in 75% with high selectivity at 60° C.

Abstract: A new N-heterocyclic catalyst system which contains N-heterocyclic carbene and amido as ligands, which are strongly bound to a palladium metal. Another heteroatom functionality can be used as a third ligand L. The NHC-amidate ligand system is unique in structure, and shows excellent reactivities in a number of chemical reactions. The chemical reactions include carbon-carbon and carbon-heteroatom (oxygen and nitrogen) bond formations, and oxidation reactions of saturated carbon chemicals via C—H activation.

Abstract: A new N-heterocyclic catalyst system which contains N-heterocyclic carbene and amido as ligands, which are strongly bound to a palladium metal. Another heteroatom functionality can be used as a third ligand L. The NHC-amidate ligand system is unique in structure, and shows excellent reactivities in a number of chemical reactions. The chemical reactions include carbon-carbon and carbon-heteroatom (oxygen and nitrogen) bond formations, and oxidation reactions of saturated carbon chemicals via C—H activation.

Abstract: Lactams, libraries of lactams, and an efficient method of synthesizing a lactam, including a &ggr;-lactam, in which an &agr;-diazoacetamide of the general structure (I) is reacted under conditions promoting intramolecular C—H insertion, for example in the presence of a rhodium salt such as Rh2(OAc)4, by which means lactams that are precursors in the synthesis of diverse natural and synthetic products, including pyrrolidinone compounds such as lactacystin, pramanicin, kainic acid, statine, AHPPA, and rolipram, are produced.

Abstract: Lactams, libraries of lactams, and an efficient method of synthesizing a lactam, including a &ggr;-lactam, in which an &agr;-diazoacetamide of the general structure (I) is reacted under conditions promoting intramolecular C—H insertion, for example in the presence of a rhodiurn salt such as Rh2(OAc)4, 1

Abstract: Lactams, libraries of lactams, and an efficient method of synthesizing a lactam, including a &ggr;-lactam, in which an a-diazoacetamide of the general structure (I) is reacted under conditions promoting intramolecular C-H insertion, for example in the presence of a rhodium salt such as Rh2(OAc)4, 1

Abstract: Efficient synthetic methods towards mixed aliphatic carbonates through the three component couplings of aliphatic alcohols, alkyl halides and carbon dioxide in the presence of cesium carbonate and tetrabutylammonium iode (TBAI). Due to their enhanced nucleophilicities, cesium alkoxides are smoothly incorporated into CO2, allowing for mild reaction conditions such as ambient temperatures and short reaction durations. Various primary and secondary substrates are compatible under the standard conditions, offering high yields, while chiral templates such as &agr;-hydroxy carbonyls are resistant to racemization.

Abstract: A method for selective mono-N-alkylation of primary amines to produce secondary amines that are substantially free of overalkylated tertiary amines and quaternary ammonium salts, under mild reaction conditions without the necessity of protecting groups. Compounds of the class of secondary amines are produced by reacting an alkyl halide with an alkyl amine in anhydrous solvent, preferably dimethyl sulfoxide or N,N-dimethylformamide, in the presence of 0.1 to 3 molar equivalents of a cesium base. Optionally, the extent and selectivity of mono-N-alkylation is enhanced by addition to the reaction mixture of a powdered molecular sieve material for removal of water produced by the reaction, and/or tetrabutylammonium iodide to promote halide exchange. The invention permits selective and efficient mono-N-alkylation of a wide variety of substrates at 23° C.

Abstract: A method of preparing carbamates of the general formula RR′—N—CO2—R″ by reacting an amine with carbon dioxide and an organic electrophile in an anhydrous solvent in the presence of a cesium base, whereby carbamate synthesis is accomplished in good yield at mild temperatures, either in solution or on a solid support, and wherein R, R′, and R″ are hydrogen, alkyl of 1-18 carbon atoms, silyl, phenyl, benzyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, allyl, or heterocycle, which are widely used as industrial products, and as intermediates in organic synthesis.