第1章　緒論(Introduction) 1

第2章　有機(jī)合成基礎(chǔ)(Basic knowledge of organic synthesis) 9
2.1　有機(jī)合成中的選擇性(Selectivity in organic synthesis) 9
2.1.1　化學(xué)選擇性(Chemoselectivity) 9
2.1.2　區(qū)域選擇性(Regioselectivity) 10
2.1.3　立體選擇性(Stereoselectivity) 11
2.2　有機(jī)合成中的官能團(tuán)化學(xué)(Functional group chemistry in organic synthesis) 12
2.2.1　官能團(tuán)化(Functionalization) 12
2.2.2　官能團(tuán)轉(zhuǎn)化(Interconversion of functional group) 14
2.3　逆合成分析術(shù)語與基礎(chǔ)(Terminology and base of retrosynthetic analysis) 18
2.3.1　切斷的策略(Strategy of disconnection) 18
2.3.2　合成子與合成等價體(Synthons and synthetic equivalent) 19
2.4　親電和親核試劑概述(Overview of electrophilic reagent and nucleophilic reagent) 20
2.4.1　親電試劑概述(Overview of electrophilic reagent) 20
2.4.2　親核試劑概述(Overview of nucleophilic reagent) 24

第3章　有機(jī)金屬化合物參與的碳-碳鍵的形成 (Formation of carbon-carbon bond involving organometallic compound) 35
3.1　格氏試劑與碳-碳鍵形成 (Grignard reagent and formation of carbon-carbon bond) 35
3.1.1　格氏試劑的制備 (Preparation of Grignard reagent) 35
3.1.2　格氏試劑的反應(yīng) (Reaction of Grignard reagent) 36
3.2　有機(jī)鋰試劑與碳-碳鍵形成 (Organolithium reagent and formation of carbon-carbon bond) 43
3.2.1　有機(jī)鋰試劑的制備 (Preparation of organolithium reagent) 43
3.2.2　有機(jī)鋰試劑的反應(yīng) (Reaction of organolithium reagent) 44
3.3　有機(jī)鋅和有機(jī)鎘試劑與碳-碳鍵形成 (Organozinc/organocadmium reagents in formation of carbon-carbon bond) 45
3.3.1　有機(jī)鋅試劑的制備 (Preparation of organozinc reagent) 45
3.3.2　有機(jī)鋅試劑的反應(yīng) (Reaction of organozinc reagent) 46
3.3.3　有機(jī)鎘試劑的反應(yīng) (Reaction of organocadmium reagent) 49
3.4　有機(jī)銅(Ⅰ) 試劑與碳-碳鍵形成[Organocopper(Ⅰ) reagent and formation of carbon-carbon bond] 49
3.4.1　有機(jī)銅(Ⅰ)試劑的制備[Preparation of organocopper(Ⅰ)reagent] 49
3.4.2　有機(jī)銅(Ⅰ)試劑的反應(yīng)[Reaction of organocopper(Ⅰ)reagent] 49
3.5　有機(jī)錫試劑與碳-碳鍵形成 (Organotin reagent and formation of carbon-carbon bond) 53
3.6　有機(jī)準(zhǔn)金屬試劑與碳-碳鍵形成 (Organometalloid reagent and formation of carbon-carbon bond) 54

第4章　穩(wěn)定的碳負(fù)離子和親核試劑反應(yīng)生成碳-碳鍵(Formation of carbon-carbon bond by reaction of stabilized carbanion and nucleophile) 63
4.1　碳負(fù)離子的形成(Formation of carbanion) 63
4.1.1　由活潑亞甲基形成的碳負(fù)離子(Carbanion generated from active methylene) 63
4.1.2　被一個-C 基團(tuán)穩(wěn)定的碳負(fù)離子 (Carbanions stabilized by one -C group) 64
4.1.3　形成碳負(fù)離子常用的堿(Commonly used bases for forming carbanion) 65
4.2　碳負(fù)離子的烷基化反應(yīng)(Alkylation of carbanion) 65
4.2.1　活潑亞甲基化合物的烷基化(Alkylation of active methylene compound) 66
4.2.2　烷基化產(chǎn)物的水解 (Hydrolysis of the alkylated product) 69
4.2.3　單-C 基團(tuán)穩(wěn)定的碳負(fù)離子的烷基化(Alkylation of carbanion stabilized by one -C group) 70
4.2.4　間接法合成α-烷基醛和酮(Indirect synthesis of α-alkylated aldehyde and ketone) 72
4.3　碳負(fù)離子的�；�化反應(yīng)(Acylation of carbanion) 74
4.3.1　活潑亞甲基化合物的�；�化(Acylation of active methylene compound) 74
4.3.2　單-C 基團(tuán)穩(wěn)定的碳負(fù)離子的�；�化(Acylation of carbanion stabilized by one -C group) 76
4.4　碳負(fù)離子的縮合反應(yīng)(Condensation reaction of carbanion) 78
4.4.1　活潑亞甲基化合物的縮合反應(yīng)(Condensation reaction of active methylene compound) 78
4.4.2　與α,β-不飽和體系發(fā)生邁克爾反應(yīng)(Micheal reaction with α,β-unsaturated system) 81
4.4.3　單-C 基團(tuán)穩(wěn)定的碳負(fù)離子的縮合反應(yīng)(Condensation reaction of carbanion tabilized by one -C group) 82
4.5　被磷或硫穩(wěn)定的碳負(fù)離子(Carbanion stabilized by phosphorus or sulfur) 87
4.5.1　磷葉立德與維蒂希反應(yīng)(Phosphorus ylide and Wittig reaction) 87
4.5.2　硫葉立德(Sulfur ylide) 90

第5章　有機(jī)合成中的氧化反應(yīng)(Oxidation reactions in organic synthesis) 99
5.1　有機(jī)氧化基礎(chǔ)知識(Basic knowledge of organic oxidation reaction) 99
5.2　無機(jī)氧化劑(Inorganic oxidant) 100
5.2.1　鉻氧化劑(Chromium oxidant) 100
5.2.2　錳氧化劑(Manganese oxidant) 104
5.2.3　四氧化鋨(OsO4) 105
5.2.4　高碘酸 (Periodic acid) 106
5.2.5　四乙酸鉛[Pb(OAc)4] 106
5.2.6　臭氧(Ozone) 107
5.2.7　二氧化硒(SeO2 ) 108
5.2.8　鹵素(Halogen) 109
5.3　有機(jī)氧化劑 (Organic oxidant) 110
5.3.1　過氧酸(Peroxy acid) 110
5.3.2　二甲基亞砜 (Dimethyl sulfoxide) 114
5.3.3　奧彭瑙爾反應(yīng)(Oppenauer reaction) 115
5.3.4　坎尼扎羅反應(yīng)(Cannizzaro reaction) 116

第6章　有機(jī)合成中的還原反應(yīng)(Reduction reactions in organic synthesis) 122
6.1　有機(jī)還原反應(yīng)的類型(Types of organic reduction reactions) 122
6.1.1　催化氫化 (Catalytic hydrogenation) 123
6.1.2　金屬氫化物還原 (Metal hydride reduction) 126
6.1.3　電子轉(zhuǎn)移反應(yīng)(Electron transfer reaction) 128
6.2　常見官能團(tuán)的還原(Reduction of common functional groups) 129
6.2.1　烯烴的還原(Reduction of alkene) 129
6.2.2　炔烴的還原(Reduction of alkyne) 130
6.2.3　醛和酮的還原(Reduction of aldehyde and ketone) 130
6.2.4　羧酸及其衍生物的還原(Redaction of carboxylic acids and their derivatives) 135
6.2.5　腈的還原(Reduction of nitrile) 136
6.2.6　亞胺的還原 (Reduction of imine) 136
6.3　碳-雜原子鍵的還原斷裂(Reductive cleavage of carbon-heteroatom bond) 137

第7章　有機(jī)合成中的環(huán)化反應(yīng)(Cyclization reactions in organic synthesis) 143
7.1　環(huán)化概述與策略(Introduction and strategy of cyclization reaction) 143
7.2　非環(huán)前體的環(huán)化反應(yīng)(Cyclization reaction of non-cyclic precursor) 145
7.2.1　環(huán)的大小與反應(yīng)速率(Ring size and reaction rate) 145
7.2.2　Baldwin 規(guī)則(Baldwin rules) 145
7.2.3　陰離子環(huán)化反應(yīng)(Anionic cyclization reaction) 149
7.2.4　陽離子環(huán)化反應(yīng)(Cationic cyclization reaction) 150
7.2.5　自由基環(huán)化反應(yīng)(Free radical cyclization reaction) 152
7.3　雙邊環(huán)化與環(huán)加成反應(yīng)(Bilateral cyclization and cycloaddition reaction) 152
7.3.1　六元環(huán)的形成(Formation of six-membered ring) 153
7.3.2　五元環(huán)的形成(Formation of five-membered ring) 158
7.3.3　四元環(huán)的形成(Formation of four-membered ring) 161
7.3.4　三元環(huán)的形成(Formation of three-membered ring) 162
7.3.5　中環(huán)和大環(huán)的形成(Formation of middle and big rings) 164
7.4　芳香族雜環(huán)的合成(Synthesis of aromatic heterocycle) 165
7.4.1　五元雜環(huán)的合成(Synthesis of five-membered heterocycle) 165
7.4.2　六元雜環(huán)的合成(Synthesis of six-membered heterocycle) 169
7.4.3　六元稠雜環(huán)化合物的合成(Synthesis of six-membered fused heterocyclic compound) 171

第8章　有機(jī)合成中的保護(hù)基(Protecting groups in organic synthesis) 178
8.1　保護(hù)基的基礎(chǔ)知識(Basic knowledge of protecting groups) 178
8.2　羥基的保護(hù)(Protection of hydroxyl group) 179
8.2.1　生成醚來保護(hù)羥基(Protecting hydroxyl group by forming ether) 179
8.2.2　生成酯來保護(hù)羥基(Protecting hydroxyl group by forming ester) 182
8.3　羧基的保護(hù)(Protection of carboxyl group) 183
8.3.1　 生成酯來保護(hù)羧基(Protecting carboxyl group by forming ester) 184
8.3.2　生成原酸酯來保護(hù)羧基(Protecting carboxyl group by forming ortho ester) 186
8.4　羰基的保護(hù)(Protection of carbonyl group) 187
8.4.1　O,O-縮醛( 酮) 保護(hù)基(Protecting groups of O,O-acetal or O,O-ketal) 187
8.4.2　S， S-縮醛( 酮) 保護(hù)基(Protecting groups of S， S-acetal or S， S-ketal) 189
8.5　1,2-和1,3-二醇的保護(hù)(Protection of 1,2-and 1,3-diol) 191
8.6　氨基的保護(hù)(Protection of amino group) 192
8.6.1　叔丁氧羰基(t-Butyloxycarbonyl) 194
8.6.2　芐氧羰基(Carbobenzyloxy) 194
8.6.3　9-芴甲氧基羰基(9-Fluorenylmethyloxycarbonyl) 195

第9章　有機(jī)合成中的芳香環(huán)取代反應(yīng)(Aromatic substitution reaction in organic synthesis) 201
9.1　親電芳香取代(Electrophilic aromatic substitution) 202
9.1.1　傅-克烷基化(Friedel-Crafts alkylation) 202
9.1.2　傅-克�；�化(Friedel-Crafts acylation) 206
9.1.3　其他烷基化和�；�反應(yīng)(Other alkylation and acylation reactions) 208
9.1.4　鹵化(Halogenation) 209
9.1.5　硝化(Nitration) 212
9.2　親核芳香取代(Nucleophilic aromatic substitution) 216
9.2.1　芳基重氮離子中間體的還原脫氮(Reductive denitrification of aryldiazonium ion intermediate) 217
9.2.2　由芳基重氮離子中間體合成苯酚(Phenol from aryldiazonium ion intermediate) 217
9.2.3　由芳基重氮離子中間體合成芳基鹵化物(Aryl halide from aryldiazonium ion intermediate) 218

第10章　切斷法(Disconnection approach) 224
10.1　單官能團(tuán)醇的C—C 鍵的切斷(C—C disconnection of monofunctional alcohol) 225
10.1.1　C—C 鍵的1,1-切斷合成醇(1,1-C—C disconnection: the synthesis of alcohol) 226
10.1.2　C—C 鍵的1,2-切斷合成醇(1,2-C—C disconnection: the synthesis of alcohol) 227
10.1.3　醇和相關(guān)化合物的合成實例(Example of the synthesis of alcohol and related compound) 227
10.2　單官能團(tuán)羰基化合物C— C 鍵的切斷(C— C bond disconnection of monofu-nctional carbonyl compound) 229
10.2.1　碳負(fù)離子的�；�化制備羰基化合物（Preparation of carbonyl compound by acylation of carbanion） 230
10.2.2　碳負(fù)離子的烷基化(Alkylation of carbanion) 232
10.2.3　炔烴的氧化(Oxidation of alkyne) 234
10.3　單官能團(tuán)化合物的C=C 鍵的切斷(C=C bond disconnection of monofunc-tional compound) 235
10.3.1　消除反應(yīng)(Elimination reaction) 235
10.3.2　Wittig 反應(yīng)(Wittig reaction) 237
10.3.3　炔烴的還原(Reduction of alkyne) 238
10.4　1,2-雙官能團(tuán)化合物的切斷(Disconnection of 1,2-difunctional compound) 239
10.4.1　酰基負(fù)離子等價物(Acyl anion equivalent) 239
10.4.2　烯烴制備1,2-雙官能團(tuán)化合物(Preparation of 1,2-difunctional compound by alkene) 241
10.5　1,3-雙官能團(tuán)化合物的切斷(Disconnection of 1,3-difunctional compound) 242
10.5.1　β-羥基羰基化合物的合成(Synthesis of β-hydroxy carbonyl compound) 242
10.5.2　α,β-不飽和羰基化合物的合成(Synthesis of α,β-unsaturated carbonyl compound) 244
10.5.3　1,3-二羰基化合物的合成(Synthesis of 1,3-dicarbonyl compound) 246
10.6　1,4-雙官能團(tuán)化合物的切斷(Disconnection of 1,4-difunctional compound) 247
10.6.1　α-鹵代酮作反常極性合成子制備1,4-雙官能團(tuán)化合物(Synthesis of 1,4-difunctional compound by using α-haloketone as unnatural polarity synthon) 248
10.6.2　�；�陰離子等價物的共軛加成(Conjugate addition of acyl anion equivalent) 249
10.6.3　4-羥基酮化合物切斷為環(huán)氧化合物(Disconnection of 4-hydroxyketone into epoxid) 249
10.7　1,5-雙官能團(tuán)化合物的切斷(Disconnection of 1,5-difunctional compound) 250
10.7.1　特定碳負(fù)離子等價物的Michael 加成(Micheal addition of specific carbanion equivalent) 250
10.7.2　羅賓遜環(huán)化反應(yīng)(Robinson annelation) 253
10.7.3　1,5-二羰基化合物制備雜環(huán)(Synthesis of heterocycle by 1,5-dicarbonyl compound) 254
10.8　1,6-二羰基化合物的切斷(Disconnection of 1,6-dicarbonyl compound) 254
10.8.1　環(huán)己烯氧化(Oxidation of cyclohexene) 255
10.8.2　Diels-Alder 反應(yīng)(Diels-Alder reaction) 255
10.8.3　 Baeyer-Villiger 反應(yīng)(Baeyer-Villiger reaction) 256
10.9　芳香族化合物的切斷(Disconnection of aromatic compound) 257

第11章　不對稱合成(Asymmetric synthesis) 264
11.1　基礎(chǔ)知識與分析方法（Basic knowledge and analytical method） 264
11.1.1　手性（Chirality） 264
11.1.2　不對稱合成中的一些術(shù)語（Terms in asymmetric synthesis） 267
11.1.3　對映體組成的測定（Determination of enantiomeric composition） 269
11.2　獲得手性化合物的策略（Strategies for obtaining chiral compound） 271
11.3　第一代方法：使用手性底物（First generation method: using chiral substrate） 272
11.4　第二代方法：采用手性助劑（Second generation method: using chiral auxiliary） 274
11.5　第三代方法：采用手性試劑（Third generation method: using chiral reagent） 275
11.6　第四代方法: 不對稱催化（Fourth generation method: asymmetric catalysis） 276
11.6.1　金屬催化劑（Metal catalyst） 277
11.6.2　酶催化劑（Enzyme catalyst） 282
11.6.3　有機(jī)小分子催化劑（Organic small molecule catalyst） 283