14072-82-3Relevant academic research and scientific papers
The Interaction of π orbitals with a carbocation over three σ bonds
Lambert, Joseph B.,Ciro, Sol M.
, p. 1940 - 1945 (2007/10/03)
The semi-π analogue of double hyperconjugation ("hyperconjugation/conjugation") has been examined in 4-isopropylidenecyclohexyl mesylate (4-OMs) by comparison with the saturated analogue, trans-4-isopropylcyclohexyl mesylate (5-OMs). The unsaturated substrate reacts in 97% trifluoroethanol only four times faster than the saturated substrate. Raber-Harris plots indicate that both substrates react by ks mechanisms; i.e., solvolysis occurs with solvent assistance rather than carbocation formation. These results are consistent with the absence of a direct, through-bond interaction of the double bond with the reactive center. The absence is caused at least in part by less than ideal overlap of the γ,δ π orbitals with the α,β σ orbitals. In contrast, an electron-rich tin atom attached to the 4-position provides a large rate enhancement and changes the mechanism to carbocation formation through double hyperconjugation.
Efficient transfer-dehydrogenation of alkanes catalyzed by rhodium trimethylphosphine complexes under dihydrogen atmosphere
Maguire, John A.,Petrillo, Angelo,Goldman, Alan S.
, p. 9492 - 9498 (2007/10/02)
RhL2Cl(CO) (1; L = PMe3), a known catalyst for the photodehydrogenation of alkanes, is found to catalyze the highly efficient thermal (nonphotochemical) transfer-dehydrogenation of alkanes under high-pressure hydrogen atmosphere. The proposed mechanism involves addition of H2, loss of CO, and transfer of H2 to a sacrificial acceptor, thereby generating RhL2Cl, the same catalytically active fragment formed by photolysis of 1. Consistent with this proposal, we report that photochemically inactive species, RhL2ClL′ (L′ = P'Pr3, PCy3, PMe3) and [RhL2Cl]2, are also thermochemical catalyst precursors. These species demonstrate much greater catalytic activity than RhL2Cl(CO), particularly under moderate hydrogen pressures (ca. 500 times greater under 800 Torr of H2 at 50°C). The dependence of the turnover rates on hydrogen pressure is consistent with the proposed role of hydrogen, i.e., displacement of L′ from the four-coordinate complexes or fragmentation of H2Rh2L4Cl2, giving H2RhL2Cl, which is dehydrogenated by olefin to give RhL2Cl. Selectivity studies provide further support for the characterization of the active fragment.
Photochemical Dehydrogenation of Alkanes Catalyzed by trans-Carbonylchlorobis(trimethylphosphine)rhodium: Aspects of Selectivity and Mechanism
Maguire, John A.,Boese, William T.,Goldman, Alan S.
, p. 7088 - 7093 (2007/10/02)
The photochemical dehydrogenation of alkanes is catalyzed in solution by trans-Rh(PMe3)2(CO)Cl with high efficiency; quantum yields up to 0.10 and turnover numbers as high as 5000 are achieved with cyclooctane as substrate.The intramolecular regioselectivity of the reaction is investigated with methyl-, ethyl-, and isopropylcyclohexane.In competition experiments, cyclooctane is found to be 17 times as reactive as cyclohexane; under carbon monoxide atmosphere, the selectivity is enhanced to a factor of 130.A kinetic isotope effect, kH/kD=5.3, is found for thedehydrogenation of C6H12/C6D12.Both intra- and intermolecular selectivities are consistent with a pathway involving a reversible C-H oxidative addition followed by a β-hydrogen elimination. trans-Rh(PMe3)2(CO)Cl is demonstrated to be the only significant photoactive species in solution.The dehydrogenation reaction is quenched by carbon monoxide with Stern-Volmer kinetics.On the basis of these results, a mechanism is proposed in which the enrgy needed to drive these thermodynamically unfavorable dehydrogenations is obtained only from Rh-CO bond photolysis.
A New Reducing System: Calcium Metal in Amines. Reduction of Aromatic Hydrocarbons
Benkeser, Robert A.,Belmonte, Frank G.,Kang, Jahyo
, p. 2796 - 2802 (2007/10/02)
A new reducing system consisting of calcium dissolved in a mixture of amines (methylamine-ethylenediamine) is described.Representative aromatic hydrocarbons have been reduced by this new reagent largely to monoalkenes.Hydrocarbons like tetralin, m- and p-xylene, and indan are reduced in excellent yields by the calcium system to a crude product containing 88percent or better of a single alkene.A new technique involving oxymercuration-demercuration is used to purify two of the monoalkene isomer mixtures obtained in these reductions.Unexpectedly, durene is reduced by the calcium reagent to 1,2,4,5-tetramethyl-1,4-cyclohexadiene in excellent yield.Likewise anthracene is reduced in one step to 1,2,3,4,5,6,7,8,9,10-decahydroanthracene.Experiments designed to elucidate why the calcium system does not reduce durene or anthracene to monoalkenes are described.Similarities and differences between the calcium-amine and the lithium-amine reducing systems are discussed.
