Modern Physical Organic Chemistry

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21 Sep 2005 ... Texts dealing with physical organic chemistry. “Modern Physical Organic Chemistry”, Anslyn and Dougherty, University Science Books, 2006.
Texts dealing with physical organic chemistry “Modern Physical Organic Chemistry”, Anslyn and Dougherty, University Science Books, 2006 (www.uscibooks.com) “Determination of Organic Reaction Mechanisms, B. K. Carpenter, Wiley Interscience, 1984 “Reactive Molecules, The Neutral Reactive Intermediates in Organic Chemistry”, C. Wentrup, WileyInterscience, 1984 Historical views and perspective on the field Streitweiser’s views on physical organic chemistry http://www.iupac.org/publications/pac/1997/pdf/6902x0281.pdf Hammond’s views http://www.iupac.org/publications/pac/1997/pdf/6909x1919.pdf

terms used in ‘the field’ glossary of terms used in physical organic chemistry http://www.chem.qmul.ac.uk/iupac/gtpoc/ IUPAC phys org http://www.iupac.org/publications/pac/special/0297/

important conference in the field phys org Gordon conference summer of 2005 http://www.grc.uri.edu/programs/2005/physorg.htm

Electron pushing – from Prof. H. J. Reich (U WI) http://www.chem.wisc.edu/areas/reich/Handouts/ElecPush/epush-1.HTM (and associated links) and, from the University of Aberdeen, http://www.abdn.ac.uk/curly-arrows/org/curl.htm kinetics - thermodynamics reaction kinetics your text by Clayden, etal, as well as chapters 7 & 8 of “Modern Physical Organic Chemistry” by Dougherty and Anslyn; University Science Books, copyright 2006 (available now. See: www.uscibooks.com. It’s a stand-alone text that meant to be covered in a full year course; it is wellworth having on your bookshelf. http://www.cop.ufl.edu/safezone/prokai/pha5110/kinetics.htm kinetics vs thermodynamic control http://www.hut.fi/Yksikot/Orgaaninen/Opetus/fysikaalinen/luentomateriaali/1_luento/3_Kinetics_vs_ther modynamics.pdf Arrhenius calculation - calculator http://w3.one.net/~jwclymer/arr.html Eyring and Arrhenius equations http://www.uni-regensburg.de/Fakultaeten/nat_Fak_IV/Organische_Chemie/Didaktik/Keusch/eyr-e.htm

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Hammond postulate http://pubs.acs.org/cgi-bin/sample.cgi/jacsat/1955/77/i02/pdf/ja01607a027.pdf (G.S. Hammond’s original reference) http://pubs.acs.org/cen/science/8120/print/8120sci2.html http://www.chem.orst.edu/ch530-3/ch530/Hammond.htm http://users.ox.ac.uk/~mwalter/tutorial_web/concepts/hammonds_postulate/hammonds_postulate_page.sh tml http://www.iupac.org/goldbook/H02734.pdf Curtin-Hammett principle http://www.iupac.org/goldbook/C01480.pdf Generalized discussion – Zefirov, N. S. Tetrahedron, 1977, 33, 2719-2722 Seeman, Jeffrey I.; Farone, William A. Analytical solution to the Curtin-Hammett/Winstein-Holness kinetic system. J. Org. Chem. 1978, 43(10), 1854-64. Seeman, Jeffrey I. Effect of conformational change on reactivity in organic chemistry. Evaluations, applications, and extensions of Curtin-Hammett Winstein-Holness kinetics. Chem. Rev. 1983, 83(2), 83-134. Additional Curtin-Hammett references include, inter alia, Duan & Moeller, JACS, 2002, 124, 9368 http://www.tkk.fi/Yksikot/Orgaaninen/Opetus/fysikaalinen/luentomateriaali/1_luento/3_Kinetics_vs_ther modynamics.pdf http://www.chem.wisc.edu/areas/reich/handouts/NameEffect/Effects3.htm http://users.ox.ac.uk/~mwalter/web_04/resources/concepts/curtin_hammett_principle/curtin_hammett_pri nciple.shtml Bell-Evans-Polanyi (BEP) principle http://www.iupac.org/goldbook/B00628.pdf http://www.chem.qmul.ac.uk/iupac/gtpoc/B.html http://www3.interscience.wiley.com/cgi-bin/abstract/62004770/ABSTRACT microscopic reversibility http://www.iupac.org/goldbook/M03916.pdf http://www.iupac.org/goldbook/P04850.pdf page 1105 of Clayden text and 139-143 reactivity-selectivity principle http://www.iupac.org/goldbook/R05186.pdf http://www.iupac.org/publications/pac/1995/pdf/6705x0811.pdf http://www.chem.qmul.ac.uk/iupac/gtpoc/R.html Dynamic thermodynamic resolution (P. Beak) http://pubs.acs.org/journals/achre4/article.cgi/achre4/2000/33/i10/pdf/ar000077s.pdf Marcus equations – derivation http://www.life.uiuc.edu/crofts/bioph354/SR_Marcus_equations_solns.pdf & electron transfer http://home.uva.nl/r.m.williams/introduction-to-electron-transfer-williams-05.pdf

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Conformational analysis Conformational analysis – a video featuring Nobel Laureate Sir Derek Barton http://www.ch.ic.ac.uk/video/barton/index_qt.html Acyclic conformational analysis: http://www.courses.fas.harvard.edu/~chem206/Fall_2001/lectures/04_Acyclic_Conformational_Analysis _1/Lecture_4.pdf http://www.courses.fas.harvard.edu/~chem206/Fall_2001/lectures/05_Acyclic_Conformational_Analysis _2/Lecture_5.pdf Conformational analysis of cyclic systems: http://www.courses.fas.harvard.edu/~chem206/Fall_2001/lectures/06_Conformational_Analysis_3/Lectur e_6.pdf http://www.courses.fas.harvard.edu/~chem206/Fall_2001/lectures/07_Conformational_Analysis_4/Lectur e_07.pdf Chapter 18 (conformational analysis … see, also, the web sites), chapter 21 (formation of enols and enolates), and pages 898-900 (Zimmerman-Traxler transition states). A-values (conformational analysis - cyclohexanes) http://www.chem.wisc.edu/areas/reich/handouts/a-values/a-values.htm drawing cyclohexane http://www.chem.ucsb.edu/~little_group/teaching/109A-Little/index.shtml http://classes.yale.edu/chem125a/125/Stereo/DrawCHexane/drawcyclohexane.htm

MO theory related Hückel MO theory - calculator http://www.chem.ucalgary.ca/SHMO/#faq qualitative MO theory http://sms.kaist.ac.kr/~ischoi/bk/lecture/class%2013.pdf AM1 (= Austin method 1) calculation method (M.J.S. Dewar’s original reference) http://pubs.acs.org/cgi-bin/sample.cgi/jacsat/1985/107/i13/pdf/ja00299a024.pdf Potential energy surfaces http://www.chemsoc.org/exemplarchem/entries/2002/grant/ Textbook dealing with FMO theory - including some of the qualitative issues discussed in class today(10/24) re the polarization of MO’s as well as the Salem-Klopman equation “Frontier Orbitals and Organic Chemical Reactions”, Ian Fleming, Wiley; ISBN (paperback) 0471018198 ln(k) vs HOMO/LUMO energy gap

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Sustmann, Reiner; Schubert, Reinhard. Substituent effects in Diels-Alder additions. Angew. Chem., Int. Ed. Engl. (1972), 11(9), 840. Sustmann, Reiner. Orbital energy control of cycloaddition reactivity. 569-93.

Pure Appl. Chem. (1974), 40(4),

secondary orbital interactions Arrieta, Ana; Cossio, Fernando P.; Lecea, Begona. Direct Evaluation of Secondary Orbital Interactions in the Diels-Alder Reaction between Cyclopentadiene and Maleic Anhydride. J. Org. Chem. (2001), 66(18), 6178-6180. Garcia, Jose I.; Mayoral, Jose A.; Salvatella, Luis. Do Secondary Orbital Interactions Really Exist? Acc. Chem. Res. (2000), 33(10), 658-664.

a wonderful primer dealing with cyclic voltammetry (thermodynamic redox potentials; E’s of HOMO (oxidation) and LUMO (reduction) http://www-biol.paisley.ac.uk/marco/Enzyme_Electrode/Chapter1/Cyclic_Voltammetry1.htm#cyclic photoelectron spectroscopy (PES; Koopman’s theorem; orbital energies for bound electrons) http://www.chem.qmw.ac.uk/surfaces/scc/scat5_3.htm

hard and soft acids and bases (R.G. Pearson – original reference) http://pubs.acs.org/cgi-bin/sample.cgi/jacsat/1963/85/i22/pdf/ja00905a001.pdf

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