Transcript m - 课程中心

Welcome to Reactions and
Mechanisms in Organic
Synthesis!
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Introduction
主讲教师：马梦林
办公室：化学实验中心315室
2B-2007室
电
话： 87721078
E-mail： [email protected]
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Textbook： Guidebook to Organic Synthesis
(3rd Edition)
有机合成指南
Raymond K Mackie, David M Smith,
R Alan Aitken
世界图书出版公司 (1999)
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Reference Book:
 Modern Methods of organic synthesis (Fourth
Edition)
William Carruthers and Lain coldham
Cambridge University Press (2004)
当代有机合成方法（当代有机化学译丛）
华东理工出版社（2006）
 高等有机化学—反应和机理（BERNARD）
Bernard
华东化工学院出版社（2005）
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教学安排及成绩评定
无期中考试，期末成绩70%，课程设计20%，课堂练习10%。
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Chapter 1 Introduction
 Accomplishments of organic synthesis
in the twentieth century
 Main factors of organic synthesis
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1.Total synthesis in the nineteenth century
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1.1. The Hermann Emil Fischer
1902 Nobel Prize Winner.
“for his work on sugar and
purine syntheses .”
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2. Total Synthesis in the Twentieth Century
2.1. The Pre-World War II Era
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
Accomplishments of organic synthesis in
the twentieth century
2.2. The Woodward Era
Woodward
1965 Nobel Prize Winner.
“for his outstanding achievements in the
art of organic synthesis.”
R. B. Woodward
1917-1979
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Selected syntheses by the Woodward Group (1944 - 1981).
Ref: Angew. Chem. Int. Ed. 2000, 39, 44 – 122.
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霍夫曼 (Roald Hoffmann，1937—)
"for their theories, developed
independently, concerning the course
of chemical reactions"
威尔金森(Cerffrey Wilkinson，1921—
) pioneering work, performed
independently, on the chemistry of the
organometallic, so called sandwich
compounds"
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2.3. The Corey Era
Corey
…Corey has thus been awarded with the Prize for three
intimately connected contributions, which form a whole.
Through retrosynthetic analysis and introduction of new
synthetic reactions, he has succeeded in preparing
biologically important natural products, previously thought
impossible to achieve. Corey’s contributions have turned
the art of synthesis into a science…
Nobel Lectures: Chemistry 1981-1990, World Scientific, New Jersey, 1992, pp677-708.
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3.Selected Examples of Total Syntheses
Haemin (1929)
Penicillin (1957)
Chlorophyll a (1960)
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
Main factors of organic synthesis
• Formation of Molecular Frame
• Functionalization
• Stereochemistry of Target Molecule
Vitamin B12
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Chapter 2 Functional group
chemistry: the basics
Topics:
Selectivity of organic reactions
Functionalization (Introduction of functional group)
Interconversion of functional groups
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2.1 Selectivity of organic reactions
2.1.1
Chemoselectivity
2.1.2
Regioselectivity and regiospecificity
2.1.3
Stereoselectivity and stereospecificity
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2.2 Functionalization of alkanes
Inert to electrophilic and nucleophilic reagents
Reactive in radical reactions, particularly
halogenation
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2.3 Functionalization of alkenes
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2.4 Functionalization of alkynes
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2.5 Functionalization of aromatic hydrocarbons
2.5.1
Substitution at a ring position
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2.5.2 Reaction in the side chain

Radical substitution
Halogenation

Benzylic oxidation
See section 9.2.2 and 9.2.3
 Autoxidation
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2.6 Functionalization of substituted benzene
derivatives
Substituent
Orientation of
electrophilic substitution
Rate of substitution
relative to that of
benzene
Alkyl or aryl
o, p
Faster
-OH, -OR
o, p
Faster
-NR2, -NHR, -NR2
o, p
Faster
Halogen
o, p
Similar or slower
C=O
m
Slower
-C≡N
m
Slower
-NO2
m
Slower
-SO3H
m
Slower
-CF3
m
Slower
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2.7 Functionalization of simple heterocyclic
compounds
Please read them yourselves after school!
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2.8 Interconversion of functional groups
2.8.1 Transformation of the hydroxyl group
2.8.2 Transformation of the amino group
2.8.3 Transformation of halogeno compounds
2.8.4 Transformation of nitro and cyano compounds
2.8.5 Transformation of aldehydes and ketones
2.8.6 Transformation of acids and acid derivatives
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2.8.1 Transformation of
the hydroxyl group
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2.8.2 Transformation of the amino group
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2.8.3 Transformation of
halogeno compounds
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2.8.4 Transformation of nitro and cyano compounds
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2.8.5 Transformation
of aldehydes and ketones
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2.8.6 Transformation
of acids and acid
derivatives
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Summary
 Functionalization and interconversion of functional group
both play important parts in synthetic procedure.
 Selectivity (both regio- and stereo-) are often crucial
importance in synthetic sequence.
 Functionalization of Alkanes, alkenes and alkynes are
summarized.
 Functionalization of arenes are summarized.
 Functional group interconversions of alcohols and phenols,
amines and diazonium salts, halogeno and nitro compounds,
aldehydes and ketones, and carboxylic acids and their
derivatives, are summarized.
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