lec14_handout - Woodward-Hoffmann Rules for Cycloadditions...

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14 Massachusetts Institute of Technology Organic Chemistry 5.13 October 10, 2003 Prof. Timothy F. Jamison Notes for Lecture #14 Diels-Alder and Other Cycloaddition Reactions Molecule of the Day ferrocene "(The 1973 Nobel Prize in Chemistry is given to Ernst Otto Fischer and Geoffrey Wilkinson) for their pioneering work on the chemistry of the organometallic, so called sandwich compounds ." From the presentation of the 1973 Nobel Prize in Chemistry (For more information, see www.noble.se) Fe Cycloaddition: A pericyclic reaction in which 2 separate conjugated, overlapping arrays of orbitals combine . Cycloadditions proceed by way of a cyclic transition state , and 2 sigma bonds are formed during the course of the reaction. A suprafacial process ("s" in the table below) is one in which the bonds made or broken lie on the same face of the orbital array undergoing reaction. In an antarafacial process ("a"), the newly formed or broken bonds lie on opposite faces of the reacting orbital array.
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Unformatted text preview: Woodward-Hoffmann Rules for Cycloadditions Stereochemical Course # Electrons Thermal Mode Photochemical Mode 4n + 2 [s + s] [s + a] 4n [s + a] [s + s] Coefficients of Frontier Molecular Orbitals FMO Analysis of the "Ortho-Para Rule" and the "Alder Endo Rule" For an in-depth discussion, see I. Fleming, "Frontier Molecular Orbitals and Organic Chemical Reactions," Wiley, 1976, pp. 121-181. OMe CO 2 Me OMe OMe CO 2 Me HOMO HOMO LUMO CO 2 Me LUMO CO 2 Me OMe OMe R ignoring OMe considering OMe considering CO 2 Me ignoring CO vs. OMe overlap maximized OMe OMe etc. O OMe O OMe R MeO • Regioselectivity? "ortho-para rule" • Diastereoselectivity? "Alder endo rule" OMe OMe vs. O OMe secondary orbital interaction Note: changes to coefficients of anti-bonding orbitals are opposite those seen in bonding orbitals. consider orbitals of CO LUMO LUMO resonance hybrid description 14-2...
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lec14_handout - Woodward-Hoffmann Rules for Cycloadditions...

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