The selective, intermolecular homodimerization and cross-cycloaddition of vinylsilanes with unbiased 1,3-dienes, catalyzed by a pyridine-2,6-diimine (PDI) iron complex are described. In the absence of a diene coupling partner, vinylsilane hydroalkenylation products were obtained chemoselectively with unusual head-to-head regioselectivity (up to >98% purity, 98:2 E/Z). In the presence of a 4-or 2-substituted diene coupling partner, under otherwise identical reaction conditions, formation of value-added [2+2]- A nd [4+2]-cycloadducts, respectively, was observed. The chemoselectivity profile was distinct from that observed for analogous α-olefin dimerization and cross-reactions with 1,3-dienes. Mechanistic studies conducted with well-defined, single-component precatalysts (MePDI)Fe(L2) (where MePDI = 2,6-(2,6-Me2-C6H3Nâ CMe)2C5H3N; L2 = butadiene or 2(N2)) provided insights into the kinetic and thermodynamic factors contributing to the substrate-controlled regioselectivity for both the homodimerization and cross-cycloadditions. Diamagnetic iron diene and paramagnetic iron olefin complexes were identified as catalyst resting states, were characterized by in situ nuclear magnetic resonance and Mössbauer spectroscopic studies, and were corroborated with density functional theory calculations. Stoichiometric reactions and computational models provided evidence for a common mechanistic regime where competing steric and electronic requirements dictate the regioselectivity of oxidative cyclization. Although distinct chemoselectivity profiles were observed in cross-cycloadditions with the vinylsilane congeners of α-olefins, these products arose from metallacycles with the same connectivity. The silyl substituents ultimately governed the relative rates of β-H elimination and C-C reductive elimination to dictate final product formation.
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