20536-40-7Relevant academic research and scientific papers
Aerobic reduction of olefins by in situ generation of diimide with synthetic flavin catalysts
Imada, Yasushi,Iida, Hiroki,Kitagawa, Takahiro,Naota, Takeshi
supporting information; experimental part, p. 5908 - 5920 (2011/07/07)
A versatile reducing agent, diimide, can be generated efficiently by the aerobic oxidation of hydrazine with neutral and cationic synthetic flavin catalysts 1 and 2. This technique provides a convenient and safe method for the aerobic reduction of olefins, which proceeds with 1 equiv of hydrazine under an atmosphere of O2 or air. The synthetic advantage over the conventional gas-based method has been illustrated through high hydrazine efficiency, easy and safe handling, and characteristic chemoselectivity. Vitamin B2 derivative 6 acts as a highly practical, robust catalyst for this purpose because of its high availability and recyclability. Association complexes of 1b with dendritic 2,5-bis(acylamino)pyridine 15 exhibit unprecedented catalytic activities, with the reduction of aromatic and hydroxy olefins proceeding significantly faster when a higher-generation dendrimer is used as a host pair for the association catalysts. Contrasting retardation is observed upon similar treatment of non-aromatic or non-hydroxy olefins with the dendrimer catalysts. Control experiments and kinetic studies revealed that these catalytic reactions include two independent, anaerobic and aerobic, processes for the generation of diimide from hydrazine. Positive and negative dendrimer effects on the catalytic reactions have been ascribed to the specific inclusion of hydrazine and olefinic substrates into the enzyme-like reaction cavities of the association complex catalysts. Copyright
Halogenated Terpenoids. XXI. Concerning endo-2-Chloro-2,3,3-trimethylbicycloheptane (endo-2-Chloro-2,3,3-trimethylnorbornane: endo-Chlorocamphane)
Brecknell, Douglas J.,Carman, Raymond M.,Greenfield, Kay L.
, p. 1075 - 1080 (2007/10/02)
The stability of the title compound is discussed and attempts to synthesize it are described.
Heterogeneous Catalysis, VI. Direct Reduction of Alcohols to Hydrocarbons
Maier, Wilhelm F.,Thies, Irina,Rague Schleyer, Paul von
, p. 392 - 394 (2007/10/02)
Secondary and tertiary alcohols are converted cleanly to the parent hydrocarbons in the gas phase with H2 in the presence of a Ni/Al2O3 catalyst at 190 deg C.Primary alcohols are dehydroxymethylated; e.g., 1-hydroxymethyladamantane (4) gives adamantane (1).Alumina alone, in the absence of Ni, results in the formation of homoadamantane (5) from 4. - Keywords: Gas Phase Hydrogenolysis, Homoadamantane Preparation
SELECTIVE REDUCTION OF TERTIARY ALKYL, BENZYL, AND ALLYL HALIDES TO HYDROCARBONS USING LITHIUM 9,9-DI-N-BUTYL-9-BORABICYCLONONANATE
Toi, Hiroo,Yamamoto, Yoshinori,Sonoda, Akio,Murahashi, Shun-Ichi
, p. 2261 - 2268 (2007/10/02)
The title 9-borabicyclononane(9-BBN) ate complex (1) brings about selective removal of tertiary alkyl, benzyl, and allyl halides to give the corresponding hydrocarbons in excellent yields without concomitant attack on secondary, primary and aryl derivatives.The reduction of cis- and trans-4-t-butyl-1-methylcyclohexyl chlorides (2) with 1 gives 4-t-butyl-1-methylcyclohexanes (3) with partial inversion of configuration in cyclohexane, while that in benzene gives thermodynamically trans-3 predominantly.The reactions of 1,1-dimethyl-5-hexenyl chloride (4) and 1,7,7-trimethylbicyclohept-2-yl chloride (8) with 1 proceed with the rearrangements characteristic to a carbonium ion intermediate.The reduction of 1-ethyl-1-methylpentyl chloride with 1 follows a second-order rate equation.
