Bochum, Universiẗat, Diss., 2001.

Aziridines and cyclopropanes are valued as important building blocks for the synthesis of a wide range of organic compounds, including biologically active compounds and pharmaceuticals. The development for more efficient and cost-effective catalysts for the atom transfer reaction with olefins is a continuing area of research in both organic and inorganic chemistry. Transition metal complexes, which catalyze reactions of olefins with nitrenes and carbenes, are well-developed efficient, approaches to the direct synthesis of aziridines and cyclopropanes, but traditionally rely on expensive synthetic methods. As part of our efforts in the catalytic formation of C—C and C—N bonds, herein we show the development of a new and efficient copper(II) catalysts that exhibits high reactivity forming cyclopropanes and aziridines from a range of olefins. These catalytic systems have also shown a propensity to conduct these atom-transfer reactions in aqueous solutions, affording the opportunity to use bio-macromolecules, like DNA, to induce enantioselectivity.

No description available.

A new protocol for direct amination of N-Methyl-2-phenylindole catalyzed by copper(II) trifluoromethanesulfonate was presented. Both of (E)-N-(1,1'-Dimethyl-2,2' -diphenyl-2,3'-biindolin-3-ylidene)-4-methylbenzenesulfonamide¡]4¡^and 4-methyl -N-(1-methyl-2-phenyl-1H-indol-3-yl)benzenesulfonamide¡]2¡^were obtained under the optimal reaction conditions (2.5 mol% Cu(OTf)2, 1.2 equiv PhI=O, 0.7 equiv PhI=NTs heated at 25 ¢J in acetonitrile for 1 hour) in 78 % and 11 % yields, respectively. In addition, (E)-N-(2-hydroxy-1-methyl-2-phenylindolin-3-ylidene)-4-methylbenzene sulfonamide ¡]6¡^and (E)-N-(1,1'-dimethyl-2,2'-diphenyl-2,3'-biindolin-3-ylidene) -4-methylbenzenesulfonamide ¡]4¡^were synthesized in 47 % and 24 % yields, respectively, by using 5 mol% Cu(OTf)2, 2 equiv PhI=O, 1.2 equiv PhI=NTs at ambient temperature in acetonitrile for 1 hour. Finally, 4-methyl-N-(1-methyl-2-oxo-3-phenyl indolin-3-yl)benzenesulfonamide ¡]3¡^and 1,1'-dimethyl-2,2'-diphenyl-2,3'-biindolin -3-one ¡]7¡^can be formed under the following reaction condition, 5 mol% Cu(OTf)2, 2 equiv PhI=O, 1.2 equiv PhI=NTs and 3 equiv Ag2CO3 heated at 100 ¢J in acetonitrile for 1 hour, in 41% and 22% yields, respectively.

Flash vacuum pyrolysis (FVP) of 2-azidocycloheptanone gave two products: 3,4,5,6-tetrahydro-1H-azocin-2-one and 1-hydroxy-2-oxo-4- azabicyclo[5.3.0]dec-4-ene-3-spiro-2¡¦-cycloheptanone. Flash vacuum pyrolysis of 2-[2-(4-methoxyphenyl)vinyl]benzofuran gave two products: 4-(2-benzofuran-2-ylvinyl)phenol and 1H-6-oxacyclopenta[c]fluorine.

Flash vacuum pyrolysis (FVP) of 1-azidoindene, which via a nitrene intermediate, gave some products of rearrangement¡Gquinoline¡Bisoquinoline and 1-methylene-1H-isoindole¡CUnder pyrolytic conditions, 3-(4-methoxystyryl)thiophene could get a radical intermediate and gave 3-(4-hydroxystyryl)thiophene, or it gave contractive tricyclic compounds which having signals on spectrum but inseparable, like as indene structures.

Flash vacuum pyrolysis(FVP) of azidomethylthiophene,via a nitrene intermediate,gave two products,a dimer (thienylmethylidene-thienylamine) and a trimer (N,N`-dithienyl methylidene-thienylmethylidene diamine).The trimer underwent cyclization and dehydrogenation to afford 2,4,5-trithienylimidazole. However by the same route, FVP of azidomethylbenzo[b]furan produced only a trimer(dibenzo[b]furylmethylidene-N,N'-benzo[b]furylmethyl amine).

(1) The pyrolysis of benzoic 5-benzyl-2-furoic anhydride by using SS-FVP method can obtain the ring-opened product naphthalene, and no ring-contracted product and its further derivatives. (2) Flash vacuum pyrolysis (FVP) of 2-(2-azidoethyl)thiophene, via a nitrene intermediate gave 1,2-di(2-thienyl)ethane, 3,5-di(2-thienyl)pyridine, and 2-methylthiophene as the main products.

(1) Flash vacuum pyrolysis (FVP) of (5-methyl-2-selenophenyl)methyl benzoate gave 4-methylene-4H-selenopyran. The structure was confirmed by trapping experiment. The mechanism for the 4-methylene-4H-selenopyran will be discussed. (2) Flash vacuum pyrolysis of 2-Azidomethylselenophene, via a nitrene intermediate, gave a trimer (N,N¡¦-di-2-selenophenylmethylidene-2-selenophenylmethylidene diamine).

Flash vacuum pyrolysis (FVP) of 2-azidoacetophenone gave the dimer 2-benzoyl-4- phenylimidazole and the trimer: 2,3-dibenzoyl-5-phenylpyrazine. Flash vacuum pyrolysis of 2-azido-1-(2-thienyl)ethanone gave the dimer: 2-(2-fromylthienyl)-4-(2-thienyl)imidazole and 2-formylthiophene.