Energetics and mechanism of organolanthanide-mediated aminoalkene hydroamination/cyclization. A density functional theory analysis

This contribution focuses on organolanthanide-mediated hydroamination processes and analyzes the hydroamination/cyclization of a prototypical aminoalkene, NH₂(CH₂)₃CH=CH₂, catalyzed by Cp₂LaCH(TMS)₂, using density functional theory. The reaction is found to occur in two steps, namely, cyclization to form La-C and C-N bonds, and subsequent La-C protonolysis. Calculations have been carried out for (i) insertion of the olefmic moiety into the La-N bond via a four-center transition state and (ii) protonolysis by a second substrate molecule. The cyclized amine then dissociates, thus restoring the active catalyst. DFT energy profiles have been determined for the turnover-limiting insertion of the 1-amidopent-4-ene C=C double bond into the La-NH- bond. DFT calculations of geometries and the stabilities of reactants, intermediates, and products have been analyzed. The picture that emerges involves concerted, rate-limiting, slightly endothermic insertion of the alkene fragment into the La-N(amido) bond via a highly organized, seven-membered chairlike cyclic transition state (ΔH_calcd^‡ = 11.3 kcal/mol, ΔS_calcd^‡ = -14.6 cal/mol K). The resulting cyclopentylmethyl complex then undergoes exothermic protonolysis to yield an amine-amido complex, the resting state of the catalyst. Thermodynamic and kinetic estimates are in excellent agreement with experimental data.