- CYCLOPROPANE-1,1 prime -INDENES.
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The relative concentrations of stereoisomers in product mixtures were determined as a function of time by using a combination of analytical techniques: vapor phase chromatography, polarimetry, NMR spectroscopy, and NMR spectroscopy in the presence of an optically active lanthanide shift reagent. The stereochemical reaction kinetics reveal that the Smith mechanism is not a plausible model for one-center epimerization; two trimethylenes, produced through two distinct cyclopropane C-C bond cleavages, are implicated, since all three possible one-center epimerizations are seen.
- Baldwin,Black
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- Intrinsically Safe and Shelf-Stable Diazo-Transfer Reagent for Fast Synthesis of Diazo Compounds
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We report a crystalline compound 2-azido-4,6-dimethoxy-1,3,5-triazine (ADT) as an intrinsically safe, highly efficient, and shelf-stable diazo-transfer reagent. Because the decomposition of ADT is an endothermal process (ΔH = 30.3 kJ mol-1), ADT is intrinsically nonexplosive, as proved by thermal, friction, and impact tests. The diazo-transfer reaction based on ADT gives diazo compounds in excellent yields within several minutes at room temperature. ADT is very stable upon >1 year storage under air at room temperature.
- Xie, Shibo,Yan, Ziqiang,Li, Yuanheng,Song, Qun,Ma, Mingming
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p. 10916 - 10921
(2018/09/17)
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- The reaction of diazocyclopentadienyl compounds with cyclomanganated arenes as a route to ligand-appended cymantrenes
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The thermolysis of various cyclomanganated arenes in the presence of 5-diazocyclopentadiene, 7-diazoindene or 9-diazofluorene afforded the corresponding arenes tethered with cymantrenyl, benzocymantrenyl or dibenzocymantrenyl groups in fair to good yields. This reaction implies a multi-facetted mechanism that consists of three steps: the insertion of an alkylidene moiety into a C-Mn bond, a CAr-C bond formation and several haptotropic ring-slippages. The coupling reaction has proven to be particularly efficient with Mn(CO)4 chelates derived from acetylarenes and nitrogen-containing heterocycles. In one case of a 2-phenyl-2-oxazoline complex, the coupling with 9-diazofluorene yields a new η1-dibenzocymantrene complex in which the Mn(CO)4 moiety is chelated and is part of a six-membered metallacycle. The results of this study are mainly supported by the molecular structures of nine new complexes obtained by X-ray diffraction analyses. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Djukic, Jean-Pierre,Michon, Christophe,Heiser, Dirk,Kyritsakas-Gruber, Nathalie,De Cian, Andre,Doetz, Karl Heinz,Pfeffer, Michel
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p. 2107 - 2122
(2007/10/03)
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