Organic Synthesis I

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Organic Synthesis I
1. Main text Adv. Org. Syn. (4th Ed.) Part B,
Carey Sundberg
2. Aim acquiring various reactions and
synthetic strategies to design
synthetic routes for target molecules

• 3. Other texts ref.
• Designing Organic Synthesis S. Warren
• Modern Organic Synthesis D. L. Boger
• Advanced Organic Chemistry J. March
• Modern Methods of Organic Synthesis (4th Ed.)
  W. Carruthers
• Organic Synthesis (2nd Ed.) J. Furhop, G.
  Penzlin
• Classics in Total Synthesis I, II K.C. Nicolaou
• The Logic of Chemical Synthesis E. J. Corey

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What will be covered in Org. Syn. I
Chapter 1 Alkylation carbanion Chapter 2
Reaction of Carbon Nu w/ carbonyl Chapter 3
Functional group interconversion Chapter 5
Reduction of Carbonyl etc. Chapter 7
Organometallic main group Chapter 12
Oxidation Chapter 13 Planning and Execution
Named Reactions Reaction Mechanism
Homework Selected problems from each chapter
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Reaction Mechanism (or reasonably drawn detailed
reaction pathway) is important
-- Examples --
i) esterification
ii) acetals
iii) aldol
J. Am. Chem. Soc., 1914, 36, 530
iv) Cannizzaro rxn.
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esterification
acetals
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aldol
Cannizzaro rxn.
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Classification of Organic Synthesis

• Linear Synthesis tedious, inefficient but could
  be simple
• ex.) DNA,
  Peptide Synthesizer

2. Convergent Synthesis -- economic, time
saving
3. Divergent Synthesis -- SAR, Combichem.
4. Biosynthesis driven Synthesis -- biomimetic
synthesis
5. Symmetry considered synthesis --
simplification
6. Systematic Synthetic analysis and design
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Objective of Organic Synthesis
1. Target to be conquered ---- speed, elegance
2. Structural Information ---- unambiguous
3. S. A. R. for design ---- creativity
4. Usefulness ---- economy
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Chronology of Organic Synthesis
- 19C. Europe Industry driven Dyestuff,
Aspirin
- America Weak Industry more academic
1. Cope PennState, MIT
2. Woodward creativity
3. Stork 3-dimensional world
4. Corey Logic
5. Kish managing
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Perception of a target
1. Static -- shape -- Design
2. Dynamic -- relationship -- Control
Things to Consider
1. Connectivity -- symmetry, complexity
2. Stereochemical relationship
3. Functionality -- substructures
4. Reactivity Stability -- air, heat, light,
acid, base
5. Compatibility
6. Kinetic vs. Thermodynamic relationship
7. Products -- volatile, syrup, solubility in
water, hazard, smell..
8. Characterization of the target molecules
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Synthetic Chemistry in the 21st Century
safe
simple
100 yield
One step
Ideal Synthesis
Available material
Resource efficient
Environmentally acceptable
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Beginning of Organic Chemistry
Woehler (1828)
Beginning of Organic Synthesis
Kolbe (1845)
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Stork (2001)
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a-Terpinol
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Provide a reasonable arrow-pushing mechanism for
the following reaction
Answer
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06-03-08
Provide a reasonable arrow-pushing mechanism for
the following reaction