496-11-7Relevant articles and documents
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Errington,Linstead
, p. 666,672 (1938)
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The Disproportionation of cis-Bicyclonona-3,7-diene Catalyzed by Fe(CO)5 and Cp2Fe2(CO)4
Kagayama, Takashi,Okabayashi, Shinji,Amaike, Yoichi,Matsukawa, Yasuo,Ishii, Yasutaka,Ogawa, Masaya
, p. 2297 - 2298 (1982)
cis-Bicyclonona-3,7-diene (1) was catalytically disproportionated by the use of Fe(CO)5 and Cp2Fe2(CO)4 to bicyclonon-1(6)-ene (3) and indan (4).However, the same reaction catalyzed by the use of other metal carbonyls gave merely small amount of 3 and 4, while those using Pd- and Rh-carbons yielded only 4 and the starting material, 1, respectively.
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Naidus,Mueller
, p. 1829 (1950)
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Mironov et al.
, (1971)
Reduction method of electronic salt reaction liquid and unsaturated aromatic hydrocarbon compound
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Paragraph 0084-0087, (2021/11/10)
To the reduction method, tetrahydrofuran is used as a solvent and an electron trapping agent, metal lithium is used as a reducing agent, tertiary butanol is used as a reducing agent, and the unsaturated aromatic hydrocarbon compound is reduced under -10 - 0 °C conditions. The raw material tetrahydrofuran is used in the invention. Metal lithium and tert-butyl alcohol are all conventional chemical products, and are simple and easy to obtain. After the reaction is finished, excess lithium and solvent are recovered, and directly used to realize low cost, low pollution and high yield.
Boosting homogeneous chemoselective hydrogenation of olefins mediated by a bis(silylenyl)terphenyl-nickel(0) pre-catalyst
Lücke, Marcel-Philip,Yao, Shenglai,Driess, Matthias
, p. 2909 - 2915 (2021/03/14)
The isolable chelating bis(N-heterocyclic silylenyl)-substituted terphenyl ligand [SiII(Terp)SiII] as well as its bis(phosphine) analogue [PIII(Terp)PIII] have been synthesised and fully characterised. Their reaction with Ni(cod)2(cod = cycloocta-1,5-diene) affords the corresponding 16 VE nickel(0) complexes with an intramolecularη2-arene coordination of Ni, [E(Terp)E]Ni(η2-arene) (E = PIII, SiII; arene = phenylene spacer). Due to a strong cooperativity of the Si and Ni sites in H2activation and H atom transfer, [SiII(Terp)SiII]Ni(η2-arene) mediates very effectively and chemoselectively the homogeneously catalysed hydrogenation of olefins bearing functional groups at 1 bar H2pressure and room temperature; in contrast, the bis(phosphine) analogous complex shows only poor activity. Catalytic and stoichiometric experiments revealed the important role of the η2-coordination of the Ni(0) site by the intramolecular phenylene with respect to the hydrogenation activity of [SiII(Terp)SiII]Ni(η2-arene). The mechanism has been established by kinetic measurements, including kinetic isotope effect (KIE) and Hammet-plot correlation. With this system, the currently highest performance of a homogeneous nickel-based hydrogenation catalyst of olefins (TON = 9800, TOF = 6800 h?1) could be realised.
N-Atom Deletion in Nitrogen Heterocycles
Cai, Wangshui,Guo, Ting,Li, Guigen,Lu, Hongjian,Qin, Haitao,Wang, Shuang
, p. 20678 - 20683 (2021/08/25)
Excising the nitrogen in secondary amines, and coupling the two residual fragments is a skeletal editing strategy that can be used to construct molecules with new skeletons, but which has been largely unexplored. Here we report a versatile method of N-atom excision from N-heterocycles. The process uses readily available N-heterocycles as substrates, and proceeds by N-sulfonylazidonation followed by the rearrangement of sulfamoyl azide intermediates, providing various cyclic products. Examples are provided of deletion of nitrogen from natural products, synthesis of chiral O-heterocycles from commercially available chiral β-amino alcohols, formal inert C?H functionalization through a sequence of N-directed C?H functionalization and N-atom deletion reactions in which the N-atom can serve as a traceless directing group.
