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Intramolecular reaction
About: Intramolecular reaction is a research topic. Over the lifetime, 5015 publications have been published within this topic receiving 138213 citations.
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TL;DR: Complex [Ru(F(20)-TPP)(CO)] is an active catalyst for intramolecular aziridination of unsaturated sulfonamides with PhI(OAc)(2), producing corresponding bicyclic azirids in up to 87% yield with up to 100% substrate conversion and high turnover
Abstract: Ruthenium porphyrins [Ru(F20-TPP)(CO)] (F20-TPP = 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato dianion) and [Ru(Por*)(CO)] (Por* = 5,10,15,20-tetrakis[(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracen-9-yl]porphyrinato dianion) catalyzed intramolecular amidation of sulfamate esters p-X-C6H4(CH2)2OSO2NH2 (X = Cl, Me, MeO), XC6H4(CH2)3OSO2NH2 (X = p-F, p-MeO, m-MeO), and Ar(CH2)2OSO2NH2 (Ar = naphthalen-1-yl, naphthalen-2-yl) with PhI(OAc)2 to afford the corresponding cyclic sulfamidates in up to 89% yield with up to 100% substrate conversion; up to 88% ee was attained in the asymmetric intramolecular amidation catalyzed by [Ru(Por*)(CO)]. Reaction of [Ru(F20-TPP)(CO)] with PhINSO2OCH2CCl3 (prepared by treating the sulfamate ester Cl3CCH2OSO2NH2 with PhI(OAc)2) afforded a bis(imido)ruthenium(VI) porphyrin, [RuVI(F20-TPP)(NSO2OCH2CCl3)2], in 60% yield. A mechanism involving reactive imido ruthenium porphyrin intermediate was proposed for the ruthenium porphyrin-catalyzed intramolecular...
148 citations
TL;DR: In this paper, the thermal degradation of commercial perfluoropolyethers (Fomblin Z and Y, Krytox, and Demnum) and PFPEO (perfluoropoly(ethylene oxide)) in the presence of Lewis acids (metal oxides and halides) was examined.
Abstract: Thermal degradation of commercial perfluoropolyethers (Fomblin Z and Y, Krytox, and Demnum) and PFPEO (perfluoropoly(ethylene oxide)) in the presence of Lewis acids (metal oxides and halides) was examined. It is shown that the degradation is dominated by the intramolecular disproportionation process of the following scheme RCF 2 OCF 2 (CH 2 ) 3 OR → RCOF + CF 3 (CH 2 ) 3 OR. The reaction occurs when the two oxygen atoms flanking a monomer unit of polyether chains interact with a Lewis acid site(s). The differentail charges induced at the carbons immediately outside and inside the unit cause a fluorine transdfer and effect the disproportionation process
147 citations
147 citations
TL;DR: Intramolecular addition of a boron-cyano bond across a carbon-carbon triple bond was achieved using palladium and nickel catalysts, which served as new precursors for the synthesis of highly substituted alpha,beta-unsaturated nitriles via transition-metal-catalyzed transformations.
Abstract: Intramolecular addition of a boron−cyano bond across a carbon−carbon triple bond was achieved using palladium and nickel catalysts. Cyano(diisopropylamino)boryl homopropargyl ethers underwent regio- and stereoselective 5-exo cyclization, forming five-membered cyclic boryl ethers in high yields. The cyanoboration products thus obtained served as new precursors for the synthesis of highly substituted α,β-unsaturated nitriles via transition-metal-catalyzed transformations.
147 citations
TL;DR: The adducts are prepared in excellent yields from either enantiomer of an alkoxyamino-tethered cyclopropanediester, allowing efficient access to highly substituted homochiral pyrrolidines.
Abstract: The intramolecular reaction of oxime ethers and cyclopropane diesters results in the diastereoselective formation of substituted pyrrolo-isoxazolidines which serve as precursors to the ubiquitous pyrrolidine motif. A simple reversal of addition order of catalyst and substrate results in formation of two discrete diastereomers in a highly selective and predictable manner. The adducts are prepared in excellent yields from either enantiomer of an alkoxyamino-tethered cyclopropanediester, allowing efficient access to highly substituted homochiral pyrrolidines.
147 citations