The Ohio State University, Chemistry Department Autumn 2012
Tentative Syllabus for
Chem 6420: “Stereochemistry and Conformational Analysis”
Stereoisomerism (1 lecture) – enantiomers & origin of chirality, diastereomers, absolute
configuration (R/S, M/P, D/L), relative configuration.
Resolution of Enantiomers (2 lectures) – crystallization, separation via diastereomeric
derivatives, measurement of enantiomeric purity, kinetic resolution, enzymatic resolution.
Conformational Analysis (6 lectures) – ethane, Pitzer (torsional) strain, propane, butane,
gauche interactions, pentane and syn-pentane interaction, conformations of CH3–X–Hn
(X = O, N), alkenes and carbonyl compounds, conjugated systems, esters/amides, ring
strain, cyclohexane (Asystems,
allylic strain, decalins.
Stereochemistry of Dynamic Processes (6 lectures) – prostereoisomerism, homotopic vs.
heterotopic ligands and faces, Curtin-Hammett principle and reactions of equilibrating
systems, Hammond postulate and kinetic vs. thermodynamic control, stereoselective vs.
stereospecific, cyclization reactions, Thorpe-Ingold effect, Baldwin’s rules, conformation
and reactivity in cyclohexane systems.
Stereoelectronic Effects (6 lectures) – SN2, SN2´, E2 reactions, additions to
cyclohexenes, Fürst-Plattner rule, additions to carbonyl groups (Felkin-Anh and Cram
models), facial selectivity in cyclohexanones, anomeric and exo-anomeric effect in
glycosides, 1,4-eliminations and ring expansions, halohydrin rearrangements, reactions at
benzylic carbons, acetals and esters
Chemistry 6420: Stereochemistry and Conformational Analysis (AU 2012)
1. Texts and Study Aids
1. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry, 5th Ed. Parts A and B,
Kluver Academic: New York, 2007. Also useful for Chem 6410, 6430, and 7430.
2. Carruthers, W.; Coldham, I. Modern Methods of Organic Synthesis, 4th Ed.;
Cambridge University Press: Cambridge, 2004.
3. Anslyn, E. V.; Dougherty, D. A. Modern Physical Organic Chemistry University
Science Books: Suasalito, 2006. Also useful for Chem 6410, 6430, and 7430.
4. Wyatt and Warren: Organic Synthesis, Strategy and Control, Wiley: Chichester
(2007) (web: cs-books@wiley.co.uk) ISBN 978-0-471-92963-5 (paperback)
5. Ian Fleming: Molecular Orbitals in Organic Chemical Reactions, Wiley: Chichester
(2009) (web: cs-books@wiley.co.uk) ISBN 978-0-470-74659-2 (paperback)
Good set of molecular models.
2) Brief description of the course
Fundamental principles of stereochemistry, including stereoisomerism, enantiomer resolution,
conformational analysis of C-C and C-heteroatom bonds, cyclic stereochemistry,
the stereochemistry of dynamic processes, and stereoelectronic effects.
Prereq: 2520 (253), 2620 (253), 2920H, or equiv. Not open to students with credit for 730.
3) A brief list (1 to 10 items) of the main topics that will be covered in the course
Stereoisomerism– enantiomers & origin of chirality, diastereomers, absolute
configuration (R/S, M/P, D/L), relative configuration.
Resolution of Enantiomers –crystallization, separation via diastereomeric derivatives,
measurement of enantiomeric purity, kinetic resolution, enzymatic resolution.
Conformational Analysis – ethane, Pitzer (torsional) strain, propane, butane, gauche
interactions, pentane and syn-pentane interaction, conformations of CH3–X–Hn (X =
O, N), alkenes and carbonyl compounds, conjugated systems, esters/amides, ring
strain, cyclohexane (A-values, calculation of Keq from G°), cyclohexene systems,
allylic strain, decalins.
Stereochemistry of Dynamic Processes – prostereoisomerism, homotopic vs.
heterotopic ligands and faces, Curtin-Hammett principle and reactions of
equilibrating systems, Hammond postulate and kinetic vs. thermodynamic control,
stereoselective vs. stereospecific, cyclization reactions, Thorpe-Ingold effect,
Baldwin’s rules, conformation and reactivity in cyclohexane systems.
Stereoelectronic Effects – SN2, SN2´, E2 reactions, additions to cyclohexenes, FürstPlattner rule, additions to carbonyl groups (Felkin-Anh and Cram models), facial
selectivity in cyclohexanones, anomeric and exo-anomeric effect in glycosides, 1,4eliminations and ring expansions, halohydrin rearrangements, reactions at benzylic
carbons, acetals and esters
References
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7.
Fuhrhop, J. and Li, G; Organic Synthesis; 3rd Edition, Verlag Chemie:
Weinheim, 2003.
Warren, S. Organic Synthesis: The Disconnections Approach, Wiley: New
York.
Warren, S. Workbook for Organic Synthesis: The Disconnections Approach,
Wiley: New York.
March, J. Advanced Organic Chemistry, 4th Ed.; Wiley: New York, 1992.
QD251.2.M3
House, H. O. Modern Synthetic Reactions, 2nd Ed.; Benjamin: New York, 1972.
QD262.H67
Deslongchamps, Pierre; Stereoelectronic Effects in Organic Chemistry;
Pergamon; New York, 1983. QD481.D47
Eliel, E.; Wilen, S. H. “Stereochemistry of Organic Compounds” Wiley: New
York, 1994, QD481.E42