|
PERICYCLIC REACTIONS
Dr R.M. Adlington
Michaelmas Term – Third Year ( 6 lectures)
Hückel molecular orbitals; conservation of orbital symmetry;
frontier molecular orbital theory; Woodward-Hoffmann rules.
Cycloaddition Reactions. Diels-Alder reaction: endo-preference,
Lewis acid catalysis; [2+2] cycloaddition of ketenes, dipolar
cycloaddition, chelotropic reactions; photochemical reactions.
Electrocyclic Reactions. ring opening of cyclobutenes, ring
closure of hexatrienes, cyclopropyl halide solvolysis; charged
systems. Sigmatropic Rearrangements. Dewar method compared
to FMO approach, [1,n] H-atom shifts, Cope and Claisen variants.
Group Transfer Reactions. ene reaction variants. Applications
of pericyclic reactions in synthesis.
Bibliography
Fleming Pericyclic Reactions (Oxford Chemistry
Primer #67)
Fleming Frontier Orbitals and Organic Chemical Reactions
Gilchrist & Storr Organic Reactions and Orbital Symmetry
(> 2nd ed.)
Woodward & Hoffmann The Conservation of Orbital Symmetry
(cf. Angew. Chem., Int. Ed. Engl., 1969, 8, 781)
Isaacs Physical Organic Chemistry (2nd ed.; Ch. 14)
Lowry & Richardson Mechanism and Theory in Organic Chemistry
(3rd ed.; Chs. 10 & 11)
Jones Physical and Mechanistic Organic Chemistry (2nd ed.;
Chs. 6 & 16)
Carey & Sundberg Advanced Organic Chemistry (3rd ed.;
A: Ch. 11; B: Ch. 6)
Salem Chemistry in Britain, 1969, 5, 449
Fukui Accounts of Chemical Research, 1971, 57
|
