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Welcome to the website for CHEM 532, Fall 2009
Advanced Physical Organic Chemistry
General messages:
Happy Thanksgiving to all!
As indicated on the
syllabus, there is NO CLASS on Fri., Nov. 20.
Class resumes Mon., Nov. 30.
Midterm Exam 2 grading is in progress.
Problem Set 5 is
due
on Wed., Dec. 9 at 11 am (last day of class).
The problem set will be posted below.
Midterm Exam 1 has
been graded; the key is posted below.
Exam scores: mean ± sd 70 ± 16 (n = 32).
Median 73; range 21 to 90.
27 out of 32 scores were between 61 and 90
(mean ± sd 75 ± 9, n = 27).
Previous undergraduate organic chemistry material (40 pages)
Sample pages from Weeks (Pushing Electrons)
Sample pages from Levy (Arrow Pushing in Organic Chemistry)
Grossman textbook website (U. Kentucky) - includes errata and answer keys for all problems in the book
Problem Set 1 (due Fri., Sept. 18, 11 a.m. at start of class)
Eliel pp. 780-781 (relevant for PS1 #3)
Problem Set 2 (due Mon., Oct. 5, 11 a.m. at start of class)
Problem Set 3 (due Mon., Oct. 23, 11 a.m. at start of class)
Problem Set 4 (due Mon., Nov. 16, 11 a.m. at start of class)
Problem Set 5 (due Wed., Dec. 9, 11 a.m. at start of class)
Practice Midterm Exam 1 (blank)
Midterm Exam 1 (blank): if you want to use this for practice
Practice Midterm Exam 2 (blank)
Grossman in-chapter problem 1.5 (numbered "1.4" on top of p. 24; note erratum: problem was misnumbered!)
C&S p. 809 acylium ion in Friedel-Crafts acylation
Wilder J. Org. Chem. 1975 manuscript relevant to Grossman problem 1.5
Ali J. Chem. Soc. Chem. Commun. 1980 manuscript relevant to Grossman Ch. 1 problem 4(m)
Gilbert Tetrahedron Lett. 1975 manuscript relevant to Grossman Ch. 1 problem 4(m)
Grudzinski J. Chem. Soc. Perkin Trans. 1 1975 manuscript relevant to Grossman Ch. 1 problem 4(m)
Grossman Ch. 2 problems 2(l) and (m) (Bayliss-Hillman reaction)
Grossman Ch. 2 problem 2(e) (Darzens condensation)
Grossman Ch. 2 problem 2(b) (Curtius rearrangement)
Grossman Ch. 2 problems 1(a), (c), and (k) (SRN1 reactions)
Grossman Ch. 2 problem 2(t) (benzilic acid rearrangement)
Energy & equilibrium (also energy & kinetics)
Kerber J. Chem. Educ. 2006 manuscript on resonance
Braida et al. Angew. Chem.. 2009 manuscript on Saytzeff's rule and hyperconjugation
IUPAC Compendium of Chemical Terminology (Gold Book)
Braniac video demonstration – alkali metal ions in water
Braniac video demonstration – thermite reaction
Nature 2006 article on important chemistry problems
Pure Appl. Chem. 2008 article on chemical structure standards (note structure error p. 297)
Website on Named Things in Chemistry & Physics
Sarma J. Chem. Educ. 2004 manuscript on chemical etymology
Bradley et al. J. Chem. Educ. 2002 manuscript on sophomore organic chemistry lectures
Larrick & Soll Science 2008 commentary on fuel efficiency measures (MPG)
Whangbo et al. Can J. Chem. 1975 manuscript including bond length of protonated formaldehyde
Turkenburg et al. J. Am. Chem. Soc. 1982 manuscript on SN2 reaction of cyclopropyl halides
Gleitsman et al. J. Biol. Chem. 2008 manuscript on acetylcholine receptor and double mutant cycle
Maglott et al. J. Am. Chem. Soc. 1999 manuscript with example of 3-component thermodynamic cycle
Forconi et al. Angew. Chem. Int. Ed. 2009 manuscript with example of double mutant cycle
Stolow Nature 2009 commentary on Filsinger et al. manuscript
Resonance & aromaticity
Wiberg Acc. Chem. Res. 1999 manuscript on C=O groups and resonance
Wiberg J. Chem. Educ. 1996 manuscript on C=O groups and electrostatic effects
Balaban et al. Chem. Rev. 2005 manuscript on history of aromaticity
Stanger Chem. Commun. 2009 commentary on concept of aromaticity
Siegel Angew. Chem. Int. Ed. Engl. 1994 manuscript on Mills-Nixon effect
Mohler et al. Angew. Chem. Int. Ed. Engl. 1990 manuscript on hydrogenation of central benzene ring
Starphenylene hydrogenation structures
Müller Angew. Chem. Int. Ed. 2009 commentary on Ge dication isolated within cryptand
Antiaromaticity
Fattahi et al. Angew. Chem. Int. Ed. 2006 manuscript on cyclobutadiene heat of formation
Deniz et al. Science 1999 manuscript on experimental measure of cyclobutadiene antiaromaticity
Untch & Wysocki J. Am. Chem. Soc. 1967 manuscript on [12]annulene derivative
Unusual structures related to aromaticity
Bean & Fowler Org. Lett. 2008 manuscript on stacked-ring aromaticity
Jasti et al. J. Am. Chem. Soc. 2008 manuscript on radially arranged p orbitals
Hückel/Möbius aromaticity
Yoon et al. Nat. Chem. 2009 review on Möbius aromaticity in expanded porphyrins
Jux Angew. Chem. Int. Ed. 2008 manuscript on Hückel/Möbius aromaticity and porphyrins
Saito et al. Angew. Chem. Int. Ed. 2008 manuscript on Möbius aromatic heptaphryins
Tokuji et al. J. Am. Chem. Soc. 2009 manuscript on Möbius aromatic hexaphryin
Inoue et al. Angew. Chem. Int. Ed. 2009 manuscript on Möbius aromatic hexaphryins
Tetrahedrane
Maier et al. Angew. Chem. 1978 manuscript on tetra-t-butyltetrahedrane
Maier Angew. Chem. 1988 review on tetrahedrane and cyclobutadiene
Maier et al. Angew. Chem. 2001 manuscript on tetrakis(trimethylsilyl)cyclobutadiene and tetrahedrane
Maier et al. J. Am. Chem. Soc. 2002 manuscript on tetrakis(trimethylsilyl)tetrahedrane
Sekiguchi & Tanaka J. Am. Chem. Soc. 2003 manuscript on tetrahedranyllithium
Tanaka et al. Angew. Chem. 2005 manuscript on hexakis(trimethylsilyl)tetrahedranyltetrahedrane
Baldwin's Rules
Alabugin et al. J. Am. Chem. Soc. 2008 manuscript on 5-endo-dig radical cyclization
Smith et al. ChemBioChem 2008 manuscript on 6-endo-tet enzyme-catalyzed reaction
Isomerism
Clayden et al. Angew. Chem. 2009 review of atropisomers
Rasberry & Shimizu Org. Biomol. Chem. 2009 manuscript on molecular playdough (atropisomers)
Shorafa et al. Angew. Chem. 2009 manuscript on bond-stretch isomers
Irikura J. Org. Chem. 2008 manuscript on in-adamantane
Unusual chirality
Ishida et al. Chem. Commun. 2009 manuscript on chiral imidazole
Kawabata et al. J. Am. Chem. Soc. 2009 manuscript on axially chiral binaphthyl surrogates
Schreiner et al. J. Am. Chem. Soc. 2009 manuscript on chiral alpha-helicenes
Claborn et al. Angew. Chem. 2008 manuscript on optical rotation of achiral compounds
Linear Free Energy Relationships (LFER): Hammett analysis
Hansch et al. Chem. Rev. 1991 review of Hammett parameters
Schwan J. Chem. Educ. 1993 manuscript on Hammett analysis
Hart & Sedor J. Am. Chem. Soc. 1967 manuscript on cyclodehydration of 2-phenytriarylcarbinols
Apeloig & Nakash J. Am. Chem. Soc. 1996 manuscript on phenol addition to disilene
Miller & Sigman Angew. Chem. 2008 manuscript on Taft parameters and asymmetric catalysis
Sigman & Miller J. Org. Chem. 2009 manuscript on Taft parameters and asymmetric catalysis
Kinetics
Blackmond Angew. Chem. 2009 essay on principle of microscopic reversibility
Murdoch J. Chem. Educ. 1981 manuscript on rate-limiting step
Kost & Pross Educ. in Chem. 1977 manuscript on misuse of energy profiles
Mayr & Ofial Angew. Chem. 1986 review on reactivity-selectivity principle
Mechanisms
More O'Ferrall J. Chem. Soc. B 1970 manuscript on energy diagrams
Pierrefixe et al. Angew. Chem. 2009 manuscript on hypervalent carbon and SN2 transition state
Loftfield J. Am. Chem. Soc. 1951 manuscript on the Favorskii rearrangement
Crossover experiments
Bergman Acc. Chem. Res. 1980 manuscript on binuclear dialkylcobalt complexes
Smith et al. Tetrahedron Lett. 1996 manuscript on Claisen/Cope rearrangement series
Silverman book example for enzyme-catalyzed reaction (diol dehydratase)
Acidity and basicity
Schwesinger bases (polyphosphazenes)
Catalysis
Kim et al. Angew. Chem. 2008 manuscript on steric strain and diaza-Cope rearrangement
List & Yang Science 2006 review on organocatalysis
MacMillan Nature 2008 review on organocatalysis
Nicewicz & MacMillan Science 2008 manuscript on SOMO organocatalysis
Sato et al. J. Org. Chem. 2009 manuscript on nitroalkane anomaly
Nucleophilic substitution
Krumper et al. Org. Lett. 2008 manuscript on continuum of nucleophilic substitution mechanisms
Phan et al. J. Am. Chem. Soc. 2009 manuscript on SN1 vs. SN2 mechanisms
Kubota et al. J. Org. Chem. 2009 manuscript on SNi mechanism
Carbonyl chemistry
Reetz et al. Angew. Chem. 1987 manuscript on Cram chelate intermediate
Carbocations
Bartlett & Tidwell JACS 1968 manuscript on SN1 solvolysis rates
Page 465 from L&R: 2-norbornyl carbocation, from exo versus endo
Pericyclic reactions
Wilhelm Nature 2008 commentary including "avoided crossing"
Boston Globe 2005 article on Corey/Woodward controversy
Hoffmann Angew. Chem. 2004 article on history of Woodward-Hoffmann rules
DeRosa & Arnold J. Org. Chem. 2009 manuscript on inverse electron demand Diels-Alder reaction
Cookson Chem. Commun. 1966 manuscript on [6+4] cycloaddition reaction