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Welcome to Reactions and

Mechanisms in Organic

Synthesis!

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主讲教师：马梦林主讲教师：马梦林

办公室：化学实验中心办公室：化学实验中心 315315 室室

2B-20072B-2007 室室

电 话： 电 话： 8772107887721078

E-mailE-mail ： ： mmlchem@163.com

IntroductionIntroduction

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TextbookTextbook ：：Guidebook to Organic Synthesis Guidebook to Organic Synthesis

(3(3rdrd Edition) Edition)

有机合成指南有机合成指南

Raymond K MackieRaymond K Mackie , David M S, David M S

mith, mith, R Alan AitkenR Alan Aitken

世界图书出版公司 世界图书出版公司 (1999)(1999)

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Reference Book:Reference Book: Modern Methods of organic synthesis (Fourth Modern Methods of organic synthesis (Fourth

Edition)Edition)

William Carruthers and Lain coldhamWilliam Carruthers and Lain coldham

Cambridge University Press (2004)Cambridge University Press (2004)

当代有机合成方法（当代有机合成方法（当代有机化学译丛） ）

华东理工出版社（华东理工出版社（ 20062006 ）） 高等有机化学—反应和机理（高等有机化学—反应和机理（ BERNARDBERNARD ））

Bernard

华东化工学院出版社（ 20052005 ））

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教学安排及成绩评定教学安排及成绩评定

无期中考试，期末成绩无期中考试，期末成绩 70%70% ，课程设计，课程设计 20%20% ，课堂练，课堂练习习 10%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 puri

ne 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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…Corey has thus been awarded with the Prize for three inti

mately connected contributions, which form a whole. Thro

ugh retrosynthetic analysis and introduction of new synthet

ic reactions, he has succeeded in preparing biologically im

portant natural products, previously thought impossible to

achieve. Corey’s contributions have turned the art of synth

esis into a science…

Nobel LecturesNobel Lectures: Chemistry 1981-1990, World Scientific, New Jersey, 1992, pp677-708.

2.3. The Corey Era

Corey

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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 hydrocarbons2.5.1 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

SubstituentOrientation 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 b

oth play important parts in synthetic procedure.

Selectivity (both regio- and stereo-) are often crucial import

ance in synthetic sequence.

Functionalization of Alkanes, alkenes and alkynes are sum

marized.

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 deriv

atives, are summarized.