Advanced organic chemistry - 1st quarter

Professor: R. D. Little  (little@chem.ucsb.edu )

Office: PSB-N 3649C/D
Office Hours: Tuesday’s from 3-4 pm and by appointment
Location: MWF, 11-11:50 in Phelps 1508

Copies of the texts are available in the UCSB Reserve Book Room - 1 day reserve
 

Items to Download:

The class syllabus in PDF format

Acrobat Reader 5.0 (To read PDF files.)

A few useful web sites

… are listed below.  I will add to it, or make specific reference to some of them as the quarter progresses.  Have a look at them and see what wonderful resources are available to you regarding a host of topics, including, for example those listed below as “some concepts/names”.

http://www.chem.wisc.edu/areas/organic/index-chem.htm

http://www.chem.wayne.edu/acs-organic-division/links.html
http://dmoz.org/Science/Chemistry/Organic/

named reactions, reagents, etc.
http://www.chem.wisc.edu/areas/organic/index-chem.htm
http://orgchem.chem.uconn.edu/namereact/named.html
http://www.chem.yorku.ca/NAMED/
http://www.geocities.com/chempen_software/reactions.htm
http://www.chemie.fu-berlin.de/chemistry/index/org/

Potential energy surfaces
http://www.chemsoc.org/exemplarchem/entries/2002/grant/
http://www.brunel.ac.uk/depts/chem/ch241s/re_view/gridview/paper/paper.htm

A-values (conformational analysis - cyclohexanes)
http://www.chem.wisc.edu/areas/reich/handouts/a-values/a-values.htm

palladium catalyzed reactions
http://icg.harvard.edu/~chem117/files/L11/Lecture_11.pdf

elementary spectroscopy
http://www.chem.ucla.edu/~webspectra/

important aspects of stereoselective reactions
http://icg.harvard.edu/~chem117/files/L15/Lecture_15.pdf

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

Dynamic thermodynamic resolution
http://pubs.acs.org/journals/achre4/article.cgi/achre4/2000/33/i10/pdf/ar000077s.pdf

secondary orbital interactions
“Do secondary orbital interactions really exist?” ACR 2000, 33. 658-664
 
 Hückel MO theory - calculator
http://www.chem.ucalgary.ca/SHMO/#faq

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

A 2001 review of Diels-Alder reactions
http://jbcs.sbq.org.br/jbcs/2001/vol12_n5/03.pdf


From the PG synthesis – a few items for “take home”…
The basic structural features of the PG natural products; Diels-Alder chemistry & stereochemical control in a setting that you may not previously have considered; the use of a Lewis acid to drop the dienophile LUMO energy and thereby decrease the HO/LU gap and accelerate the cycloaddition; the expressions HO- and LU-controlled processes; inverse electron and normal electron demand Diels-Alder reactions; the basic nature of a sigmatropic rearrangement (focus upon 1,5-H~ and 3,3 shifts); ketene synthon (that of 2-chloroacrylonitrile … can you think of others?); Collins reagent and its use in the oxidation of primary alcohols as well as the comparison between it and the Swern oxidation (cf the mechanism for E2 chemistry to form an alkene and elimination to form a C-O pi-bond); use of a Lewis acid to cleave a methyl ether (cf with HI cleavage that you learned in your first course in organic chemistry); Baeyer-Villiger oxidation (the basic transformation and reagents commonly used – we’ll deal with detail later); halolactonization reactions & their utility within the PG synthesis context and in determining stereochemical interrelationships; use of tin hydride chemistry for the conversion of C-I to C-H; Horner-Emmons-Wadsworth reaction; the CBS reagent (its design and use).

Problem sets

Set 1 (from Clayden, et. al.)
Chapter 2:  2,3,5,6
Chapter 4: 2,4,5,9,10
Chapters 5, 6, 7 all problems of each chapter

 Set 2 (posted 10/2/02)
        solutions to set 2 [for solutions to set 1, refer to the text solution manual)
         Don't worry about the first question.  It is not formulated in an unambiguous manner.  See problem set 6, instead.

 Set 3 (posted 10/3/02)
          solutions to set 3
           correction

 Set 4 (posted 10/4/02)
          solutions to set 4
           correction

 Set 5 (posted 10/8/02)
    solutions to set 5

 Set 6 (posted 10/09/02 - see note above re set 2)
           solutions to set 6

 exam 1

Set 7
(from Clayden, et.al.; posted 10/16/02)
Chapter 8 (acid/base):  4,5,7,14
Chapter 9 (organometallic - review): 1,2,3,5,7,8

 Set 8 (posted 10/20/02)
           solutions to set 8

 Set 9 (posted 10/28/02)
 
Set 10 (posted 11/3/02)
          Chapter 34 of Clayden, et.al.:  problems 1-8 and 10-12

Set 11 (posted 11/5/02)
           Corrections:  [a] The pdf file indicates prob set 12 - it's 11.   [b] Problem 1(c) should have an ethyl group in place of the "H" positioned at C3 of the alkene.
           solutions to set 11

Set 12 (posted 11/8/02; HMO theory applications)

            Solutions to problem set 12

Preparation for exam 2 (exam date - 11/22/02)
    There will be problems like those of [a] problem set 7 (especially ch. 8, probs 4 and 14), [b] sets 8, 9, 11, [c] problems 2, 4, 7, 8, 11, and 12 of prob set 10, and [d] problems 1 and 5 of problem set 12.  

exam 2

Solutions to exams 1 and 2

Problem set 13 (posted 11/26/02)
        solution to iodolactonization problem of set 13

Set 14 (posted 12/4/02: some simple HMO theory)
        set 14 - solutions

Preparation for final exam - [a] redo each exam and problem set.  [b] practice problems (posted 12/10/02)
         solutions (posted 12/11/02)

make up class
Saturday. Nov. 2 from 9-10:30 in PSBN room 4606

'summary' of recent topics

Some aspects of Hückel MO theory

overhead projections shown in class
copies/references/web addresses

 photoelectron spectroscopy and cyclic voltammetry - see also, web sites listed above.

 cyclic voltammetry - samarium and ytterbium(III/II)
 
  esr spectrum of 1,3-butadiene radical anion

Reading list
(I'll add to this throughout the quarter, so have a look periodically)
Copies of the texts are available in the UCSB Reserve Book Room - 1 day reserve
See also the web addresses shown above.

 reading list (partial)