Density functional theory alkenes

The protocol developed by Jacobsen and Katsuki for the salen-Mn catalyzed asymmetric epoxidation of unfunctionalized alkenes continues to dominate the field. The mechanism of the oxygen transfer has not yet been fully elucidated, although recent molecular orbital calculations based on density functional theory suggest a radical intermediate (2), whose stability and lifetime dictate the degree of cis/trans isomerization during the epoxidation <00AG(E)589>. 

Semiempirical calculations show that the approach of the dipolarophile in a head-to-head manner is 5.91 kcal/mol more favorable than the head-to-tail orientation with electron-rich alkenes (93). This difference is manifest in the ground state of resulting cycloadducts where the head-to-head adduct is 6.6 kcal/mol more stable. Similarly, the head-to-head transition state is more favorable by 3.4 kcal/mol for electron-poor alkenes, and 7.4 kcal/mol for electron-rich alkenes as calculated with density functional theory (91). This preference is also carried over into the ground-state energies of the resulting cycloadducts. 

Takeuchi, N., Kanai, Y. and Selloni, A. Surface reaction of alkynes and alkenes with H-Si(lll) A density functional theory study. Journal of the American Chemical Society 126, 15890 (2004). 

The addition of ZnBi 2 to die tandem 1,3-azaprotio cyclotransfer-cycloaddition of a ketoxime with divinyl ketone results in rate enhancement and the exclusive formation of l-aza-7-oxabicyclo[3.2.1]octan-3-ones.79 The 1,3-dipolar cycloaddition of 1-aza-l-cyclooctene 1-oxide with alkenes produces the corresponding isoxazolidines in high yields with a minimum of polymeric material.80 The cycloaddition of thiophene-2 -carbaldehyde oxime with acetonitrile and methyl acrylate produces the 1,3-dipolar adduct, substituted isoxazolidines, and not the previously reported 4 + 2-adducts.81 Density functional theory and semi-empirical methods have been used to investigate the 3 + 2-cycloaddition of azoxides with alkenes to produce 1,2,3-oxadiazolidines.82 The 3 + 2-cycloaddition of a-nitrosostyrenes (62) with 1,3-diazabuta-l,3-dienes (63) and imines produces functionalized cyclic nitrones (64) regioselectively (Scheme 22).83... 

Density functional theory studies arene chromium tricarbonyls, 5, 255 beryllium monocyclopentadienyls, 2, 75 chromium carbonyls, 5, 228 in computational chemistry, 1, 663 Cp-amido titanium complexes, 4, 464—465 diiron carbonyl complexes, 6, 222 manganese carbonyls, 5, 763 molybdenum hexacarbonyl, 5, 392 and multiconfiguration techniques, 1, 649 neutral, cationic, anionic chromium carbonyls, 5, 203-204 nickel rj2-alkene complexes, 8, 134—135 palladium NHC complexes, 8, 234 Deoxygenative coupling, carbonyls to olefins, 11, 40 (+)-4,5-Deoxyneodolabelline, via ring-closing diene metathesis, 11, 219... 

Key Words Direct propylene epoxidation. Propylene oxide, Gold, Titanium, Propene, Au/Ti catalysts. Catalysis by gold. Titanium silicalite, TS-1, Gold/TS-1, Hydrogen peroxide, Kinetics, Design of experiments, Deposition-precipitation, Ammonium nitrate, Selective oxidation, Alkene epoxidation, Density functional theory, DFT calculations, QM/MM calculations. 2008 Elsevier B.v. 

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