- Unprecedented double nucleophilic addition of a hydride at a central carbon of an η3-allyl ligand
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Treatment of η3-allyl compound [Cp 2Mo(η3-C3H5)]+ (1; Cp = η5-C5H5) with MH (M = Li, Na) resulted in reduction of the allyl ligand to give propane. Deuterium-labeling studies were used to trace the origins and fates of the hydrogen atoms. The mechanism is discussed in light of the HSAB principle. The studies showed that the formation of propane can be explained by 1,2-hydrogen migration from the central to the terminal carbon of the allyl ligand, and the subsequent double nucleophilic addition of the hydride at the central carbon.
- Minato, Makoto,Sekimizu, Ryoko,Uchida, Daisuke,Ito, Takashi
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p. 3695 - 3698
(2007/10/03)
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- On the mechanism of titanium-catalyzed cyclopropanation of esters with aliphatic organomagnesium compounds. Deuterium distribution in the reaction products of (CD3)2CHMgBr with ethyl 3-chloropropionate in the presence of titanium tetraisopropoxide
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The reaction of (CD3)2CHMgBr with ethyl 3-chloropropionate in the presence of catalytic amounts of Ti(OPr1)4 results in (E)-1-(2-chloroethyl)-3,3-dideuterio-2-trideuteriomethylcyclopropanol and (CD3)2CDH, identified by mass spectrometry. The reaction mechanism is discussed.
- Epstein,Savchenko,Kulinkovich
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p. 378 - 380
(2007/10/03)
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- Electrolysis of Potassium Butyrate in Acetonitrile. A Deuterium NMR Study
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The anodic oxidation of 2,2-dideuteriobutyrate ion in acetonitrile gives rise to radical-derived and cation-derived C3 products.By 2H FT NMR spectroscopy, the radical-derived propane and propene are found to be formed without scrambling of the label.Similarly, the products derived from the intermediate isopropyl cation, i.e., the remainder of the propene and N-isopropylamides, bear deuterium only at the terminal C-1 and C-3 positions of the C3 fragment.However, the 1:1:1 label distribution found in the N-n-propylamides and the formation of cyclopropane strongly suggest that ring closure of the n-propyl cation to rapidly scrambling pr otonated cyclopropane is an important reaction pathway.Atom scrambling at the level of protonated cyclopropane shows a large H/D isotope effect.
- Laurent, Eliane,Thomalla, Marc,Marquet, Bernard,Burger, Ulrich
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p. 4193 - 4198
(2007/10/02)
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