CHEM 634
Advanced Organic Chemistry – Synthesis and Reactivity
Fall 2015
Instructor:
Mary Watson (237 BRL, 831-1529, mpwatson@udel.edu)
Office Hours: 10:30am–12noon, Wednesdays
Lectures:
2–3:15 pm, Tu/Th, 228 ALS
Lectures will be recorded and available online through UD Capture.
Link to UD Capture: https://udcapture.udel.edu/2015f/chem634-010/
Lecture notes will be posted on the course website shortly before or
directly after lecture.
Website:
http://www.udel.edu/chem/mpwatson/mpwatson/Chem_634.html
The website will be updated regularly. Please check it
for announcements, lecture notes, problem sets,
answer keys, etc.
Textbooks:
“What I cannot create, I do not
understand.”
Richard Feynman
“It is in our genes to understand
the universe if we can, to keep
trying if we cannot, and to be
enchanted by the act of
learning all the way.”
Lewis Thomas
All texts are On Reserve in the Chemistry Library.
Required
Strategic Applications of Named Reactions in Organic Synthesis. Kurti, L.; Czako, B.
Advanced Organic Chemistry, Part B: Reactions and Synthesis. Carey, F. A.; Sundberg, R. J.
Classics in Stereoselective Synthesis. Carreira, E. M.; Kvaerno, L.
The Art of Writing Reasonable Organic Reaction Mechanisms. Grossman, R. B.
Recommended
Advanced Organic Chemistry, Part A: Structure and Mechanisms. Carey, F. A.; Sundberg, R. J.
th
March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 6 Edition. Smith, M. B.; March, J.
On Reserve in the Chemistry Library
Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2nd Edition Larock, R. C.
Stereochemistry of Organic Compounds Eliel, E.; Wilel, S. H.
Protective Groups in Organic Synthesis, 4th Ed, Greene and Wuts
Transition Metals in the Synthesis if Complex Organic Molecules, 3rd Ed, Hegedus, L. S.
The Logic of Chemical Synthesis, Corey, E. J.; Cheng, X.
Other Tools:
Molecular model kit (required & allowed on exams)
You may use any brand. Here are some recommendations:
HGS 4010/Student Set – Expensive but very nice (they are a smaller set of the same models I use – I like them
because they are pretty rigid. Be warned, however, they tend to be fragile).
http://www.maruzen.info/hgs/catalog/product_info.php?cPath=11&products_id=596
Darling Models – Cheaper, but very floppy (which is not great for studying stereochemistry).
http://www.darlingmodels.com/item--KIT-1-ISBN-0-9648837-1-6-Plastic-Box-Organic-Inorganic-Organometallic-kit_1_plastic_student.html
Grades:
Midterm 1 (10/15)
Midterm 2 (11/17)
Proposal (10/6) or Presentation (Sat, 12/5)
Problem Sets
Final Exam (TBA)
Total
200 points
200 points
150 points
150 points
300 points
1000 points
Proposal: You will prepare a 2-page independent research proposal in the format for NSF Predoctoral Graduate
Fellowships. If you are eligible for an NSF fellowship, you will submit your proposal (and the rest of the application)
by the NSF deadline (Oct 30). Instructions for your proposal will be available shortly.
Presentations: You will present on a recently developed synthetic organic method to the class on Saturday, Dec 5,
9am–3pm. You must choose a paper from the list posted next to Mary’s office door by Nov 5. Instructions for your
presentation will be available shortly.
Midterms and Final: Closed note, closed book tests (unless otherwise announced in advance). You may use your
molecular model kit. Exams will cover lecture material, problem sets, assigned reading, and current literature
discussed in class.
Problem Sets: There will be 5 problem sets. They will total 30 points each. In most cases, only representative
problems, not the entire problem set, will be graded. A key will be posted for each problem set. It is your
responsibility to make sure you understand the correct answers once the key is posted. You may work in study
groups when working on the problem sets, but each student must turn in his/her own work.
Each problem set will include questions from Grossman’s Art of Writing Organic Reaction Mechanisms book. You
are responsible for all material in this book; it will be included on the midterms and final exam.
Do not use Reaxys, SciFinder Scholar or consult the literature to find the answers, unless specifically directed to do
so.
Problem sets are due at the beginning of class on the due date. Late problem sets will not be accepted as we may
discuss the answers in class after they are due.
For problem sets, you will occasionally be asked to design synthetic routes to target compounds starting with
commercially available materials. For this class, limit these commercially available materials to those available from
Acros, Aldrich, Fisher, Strem, Alfa-Aesar, or TCI.
Regrade Requests: All regrade requests must be submitted in writing by the beginning of the next lecture after the
tests are returned. The entire exam will be regraded. If grading errors are found, the revised grade may be higher or
lower than the original score. If submitting a regrade request, do not change your test in any way; exams may be
photocopied before being returned.
Academic Dishonesty: Do not plagiarize or cheat. Any student who commits academic dishonesty will be
punished according to the University of Delaware’s guidelines (http://www.udel.edu/stuguide/0910/code.html#honesty).
CHEM 634 Course Learning Goals
After successful completion of this course, a student should be able to:
1. Understand principles of retrosynthesis and be able to splan synthetic routes to complex organic molecules (1,2)
2. Understand absolute and relative molecular stereochemistry and its importance in synthetic chemistry (1)
3. Understand the use, installation and removal of protecting groups in organic synthesis (1)
4. Be familiar with the methods and reactivity associated with alkyl groups, carbonyl groups, enolates, alkenes, alkynes,
amines, amides, esters, ethers, aromatic rings, and strained rings (1)
5. Be familiar with nucleophilic substitution chemistry, radical chemistry, methods for oxidation and reduction, elementary
organometallic chemistry, pericyclic reactivity, asymmetric catalysis, and functional group interconversion, as they
pertain to organic synthesis (1)
6. Be familiar with uses and application of major electronic databases used in organic chemistry (3,5)
7. Be familiar with major journals and publications pertaining to synthetic organic chemistry (3,5)
8. Organize and review chemical literature in a topic area and present in clear and concise oral format (3,4,10)
(*Numbers in parentheses indicate the departmental learning goals with which each course goal is aligned. Please see:
http://www.udel.edu/chem/goals.html.)
Proposed Course Outline and Readings
Date
9/1
Lecture
1
Topic
Introduction, Retrosynthetic
Analysis, Arrow Pushing
Nucleophilic Substitution
9/3
2
9/8
9/10
9/15
3
4
5
9/17
9/22
6
7
Carboxylates
Protecting Groups
Electronic Databases and
Searching the Literature
Aromatic Substitution
Transition Metal Catalysis
9/24
9/29
10/1
10/6
10/8
8
9
10
11
12
Transition Metal Catalysis
Alcohol/Ketone Oxidation
C=X Reduction
Enolates
Enolates
10/13
10/15
10/20
10/22
10/27
10/29
11/3
11/5
11/10
11/12
11/17
11/24–
11/26
12/1
12/3
SAT, 12/5,
9am
12/8
12/10
13
Aldol Reactions
Midterm 1
14
Aldol Reactions
15
Alkene Synthesis
16
Alkene Oxidation
17
Alkyne Synthesis
18
C=C Reduction
19
Radical Chemistry
20
Radical Chemistry
21
Pericyclic Reactions
Midterm 2
No class (Fall Break)
Notes
Meet in 221 BRL
Problem Set 1 due
Reading
Grossman Ch 1
Corey Ch 1–6 (handout)
CS-B 3.1–3.2
Grossman Ch 2
CS-B 3.4
CS-B 3.5
Handout
CS-B 11.1–11.2, Grossman Ch 2
Heg Ch 1–2 (handout), CS-B 7.1, 8.2–8.3,
11.3, Grossman Ch 6
Proposals due
CS-B 12.1, 12.5, 12.7
CS-B 5.3, 5.6, 5.7, 3.5 (CK 2)
CS-B 1
Problem Set 2 due
CS-B 2 (CK 4, 5)
CS-B 2.4, 4, 5.1, 5.6 (CK 7,8,9)
Problem Set 3 due
CS-B 10.3, CS-A 11, Grossman Ch 5
Problem Set 4 due
CS-B 6 (CK 16, 17,18), Grossman Ch 4
22
Pericyclic Reactions
23
Pericyclic Reactions
Presentations
24
25
Special Topics
Special Topics
Problem Set 5 due
CS = Carey and Sundberg; CK = Carreira and Kvaerno; Heg = Hegedus and Soderberg; () = optional reading