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- W2012432786 endingPage "2012" @default.
- W2012432786 startingPage "2004" @default.
- W2012432786 abstract "This contribution focuses on organolanthanide-mediated hydroalkoxylation processes and investigates the hydroalkoxylation/cyclization of a prototypical alkynyl alcohol, HO(CH2)3C≡CR, (R = H, CH3, TMS) catalyzed by the homoleptic La[N(SiMe3)2]3 amido complex using density functional theory. The reaction is found to occur in two steps, namely, cyclization with concerted Ln−C and C−O bond formation and subsequent Ln−C protonolysis. Calculations are carried out for: (i) insertion of the alkynyl moiety into the La−O bond via a four-center transition state and (ii) protonolysis by a second substrate molecule. The cyclized ether then dissociates, restoring the active catalyst. Analysis is also carried out on the effects of other Ln3+ ions and alkyne R substituents on the reaction energetics in comparison to the analogous organolanthanide-mediated aminoalkyne and aminoolefin hydroamination processes. DFT energetic profiles are computed for the turnover-limiting insertion of the alkynyl alcohol C≡C triple bond into the La−O bond, and the geometries and stabilities of reactants, intermediates, and products are analyzed. The picture that emerges involves a concerted, rate-limiting insertion of the alkyne fragment into the La−O bond via a highly organized transition state (ΔH‡calcd = 15.3 kcal/mol, ΔS‡calcd = −6.5 cal/(mol K)). The resulting cyclopentylmethylene complex then undergoes exothermic protonolysis to regenerate the active catalyst. Thermodynamic and kinetic estimates are in excellent agreement with experimental data." @default.
- W2012432786 created "2016-06-24" @default.
- W2012432786 creator A5000731301 @default.
- W2012432786 creator A5016296466 @default.
- W2012432786 creator A5044454837 @default.
- W2012432786 date "2010-04-09" @default.
- W2012432786 modified "2023-10-15" @default.
- W2012432786 title "Atom-Efficient Carbon−Oxygen Bond Formation Processes. DFT Analysis of the Intramolecular Hydroalkoxylation/Cyclization of Alkynyl Alcohols Mediated by Lanthanide Catalysts" @default.
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