There is also a secondary interaction between a lone pair orbital perpendicular to the plane of the peracid, nO(p) (HOMO) and the unoccupied π*C=C orbital (LUMO). Find more information on the Altmetric Attention Score and how the score is calculated. Corey-Chaykovsky Reaction m-Chloroperoxybenzoic acid (mCPBA) in particular is used often in laboratories because it is a relatively safe (in terms of explosiveness) solid reagent. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Thus our results provide rationale for the experimentally observed sharp increase in the enantioselectivity of epoxidation of the terminal olefins by peracids at low temperature and in the presence of neutral axial ligand N-methylmorpholine-N-oxide (33–35). We verify this assumption by studying both spin states rigorously, although quintet cis oxo species should not contribute to enantioselectivity (42). ・Henbest Rule: Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. The lowest barriers on the ground sextet-state potential energy surface in the absence of an axial ligand are 14.6 and 17.3 kcal/mol for cisON and cisNO isomers, respectively. The ground state of the MnV–trans-oxo species has been predicted to be singlet, triplet, or quintet. The relative energies of these transition state are {15.9; 17.0} and {14.8; 16.6} kcal/mol, respectively. Shi Epoxidation The ring closure in the radical intermediate has been studied by others for MnV–trans-oxo species on smaller models (5–9). One of such interactions is dispersion-type π–π interaction of the aryl-substituted olefins with the catalyst. to give an oxirane. Sharpless Epoxidation Therefore, the energetics presented below does not include zero-point energy or entropy corrections. The most important geometric isomers are trans, cisON, and cisNO and the oxidation states are II, III, and IV. Lett., 2003, 5, 3787-3790. This finding suggests that spin state may actually affect the enantioselectivity of the epoxidation. Cell-Permeant Large Stokes Shift Dyes for Transfection-Free Multicolor Nanoscopy’…’, Complex Acid Chlorides from Unsaturated Hydrocarbons’…’, Near-Infrared Light Activated Azo-BF2 Switches’…’, An Excimer-Based, Turn-On Fluorescent Sensor for the Selective Detection of Diphosphorylated Protein’…’, Small-Molecule Labeling of Live Cell Surfaces for Three-Dimensional Super-Resolution Microscopy’…’, Photoelectric Signal Conversion by Combination of Electron-Transfer Chain Catalytic Isomerization an’…’, Lighting Up Individual DNA Damage Sites by In Vitro Repair Synthesis’…’, Metal-Free Hydrogenation Catalyzed by an Air-Stable Borane: Use of Solvent as a Frustrated Lewis Bas’…’, Dual Changes in Conformation and Optical Properties of Fluorophores within a Metal−Organic Framework’…’, Far-Red Fluorescence Probe for Monitoring Singlet Oxygen during Photodynamic Therapy’…’, Accessing Zinc Monohydride Cations through Coordinative Interactions’…’, Arylazopyrazoles: Azoheteroarene Photoswitches Offering Quantitative Isomerization and Long Thermal ’…’, Quantitative Photoswitching in Bis(dithiazole)ethene Enables Modulation of Light for Encoding Optica’…’, A Mitochondria-Targetable Fluorescent Probe for Dual-Channel NO Imaging Assisted by Intracellular Cy’…’, Modulating Short Wavelength Fluorescence with Long Wavelength Light’…’, Reversible Photochromic System Based on Rhodamine B Salicylaldehyde Hydrazone Metal Complex’…’, Energy Transfer on Demand: Photoswitch-Directed Behavior of Metal–Porphyrin’…’, Persistent Antimony- and Bismuth-Centered Radicals in Solution’…’. & Kasuga, T. (1996). 1909, 42, 4811. doi:10.1002/cber.190904204100 mCPBA is a widely used reagent for this conversion, while magnesium For the MnV–trans-L-oxo species with L = acetate, the MnIV–trans-L radical intermediates in the quintet and triplet states are –16.9 and –16.8 kcal/mol, respectively, and the ring closure TS2s are –14.7 for the quintet state and slightly higher –12.3 kcal/mol for the triplet state. Energy-wise, the triplet state for the acetate and imidazole is 1.3 kcal/mol lower and 0.3 kcal/mol higher than the quintet, respectively.

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