Theoretical studies on the Mo-catalyzed asymmetric intramolecular Pauson-Khand-type [2+2+1] cycloadditions of 3-allyloxy-1-propynylphosphonates.
Density functional theory (DFT) was used to investigate the Mo-catalyzed intramolecular Pauson-Khand reaction of 3-allyloxy-1-propynylphosphonates. All intermediates and transition states were optimized completely at the B3LYP/6-31 G(d,p) level [LANL2DZ(f) for Mo]. In the Mo-catalyzed intramolecular Pauson-Khand reaction, the C–C oxidative cyclization reaction was the chirality-determining step, and the reductive elimination reaction was the rate-determining step. The carbonyl insertion reaction into the Mo–C(sp(3)) bondwas easier than into the Mo–C=C bond. And the dominant product predicted theoretically was of (S)-chirality, which agreed with experimental data. This reaction was solventd ependent, and toluene was the best among the three solvents toluene, CH3CN, and THF.
College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People’s Republic of China.
Qingxi
Q
Meng
Ming
M
Li
D000097:Acetonitriles / Q000737:chemistry; D002384:Catalysis; D003198:Computer Simulation; D061565:Cycloaddition Reaction; D005663:Furans / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D063065:Organophosphonates / Q000138:chemical synthesis* / Q000737:chemistry; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013237:Stereoisomerism; D013816:Thermodynamics; D014050:Toluene / Q000737:chemistry
D000097:Acetonitriles; D005663:Furans; D063065:Organophosphonates; D012997:Solvents; C434645:hexacarbonylmolybdenum; D014050:Toluene; C018674:tetrahydrofuran; D008982:Molybdenum; C032159:acetonitrile