包邮有机合成(马梦林)

第1章　绪论(Introduction) 1

第2章　有机合成基础(Basic knowledge of organic synthesis) 9
2.1　有机合成中的选择性(Selectivity in organic synthesis) 9
2.1.1　化学选择性(Chemoselectivity) 9
2.1.2　区域选择性(Regioselectivity) 10
2.1.3　立体选择性(Stereoselectivity) 11
2.2　有机合成中的官能团化学(Functional group chemistry in organic synthesis) 12
2.2.1　官能团化(Functionalization) 12
2.2.2　官能团转化(Interconversion of functional group) 14
2.3　逆合成分析术语与基础(Terminology and base of retrosynthetic analysis) 18
2.3.1　切断的策略(Strategy of disconnection) 18
2.3.2　合成子与合成等价体(Synthons and synthetic equivalent) 19
2.4　亲电和亲核试剂概述(Overview of electrophilic reagent and nucleophilic reagent) 20
2.4.1　亲电试剂概述(Overview of electrophilic reagent) 20
2.4.2　亲核试剂概述(Overview of nucleophilic reagent) 24

第3章　有机金属化合物参与的碳-碳键的形成 (Formation of carbon-carbon bond involving organometallic compound) 35
3.1　格氏试剂与碳-碳键形成 (Grignard reagent and formation of carbon-carbon bond) 35
3.1.1　格氏试剂的制备 (Preparation of Grignard reagent) 35
3.1.2　格氏试剂的反应 (Reaction of Grignard reagent) 36
3.2　有机锂试剂与碳-碳键形成 (Organolithium reagent and formation of carbon-carbon bond) 43
3.2.1　有机锂试剂的制备 (Preparation of organolithium reagent) 43
3.2.2　有机锂试剂的反应 (Reaction of organolithium reagent) 44
3.3　有机锌和有机镉试剂与碳-碳键形成 (Organozinc/organocadmium reagents in formation of carbon-carbon bond) 45
3.3.1　有机锌试剂的制备 (Preparation of organozinc reagent) 45
3.3.2　有机锌试剂的反应 (Reaction of organozinc reagent) 46
3.3.3　有机镉试剂的反应 (Reaction of organocadmium reagent) 49
3.4　有机铜(Ⅰ) 试剂与碳-碳键形成[Organocopper(Ⅰ) reagent and formation of carbon-carbon bond] 49
3.4.1　有机铜(Ⅰ)试剂的制备[Preparation of organocopper(Ⅰ)reagent] 49
3.4.2　有机铜(Ⅰ)试剂的反应[Reaction of organocopper(Ⅰ)reagent] 49
3.5　有机锡试剂与碳-碳键形成 (Organotin reagent and formation of carbon-carbon bond) 53
3.6　有机准金属试剂与碳-碳键形成 (Organometalloid reagent and formation of carbon-carbon bond) 54

第4章　稳定的碳负离子和亲核试剂反应生成碳-碳键(Formation of carbon-carbon bond by reaction of stabilized carbanion and nucleophile) 63
4.1　碳负离子的形成(Formation of carbanion) 63
4.1.1　由活泼亚甲基形成的碳负离子(Carbanion generated from active methylene) 63
4.1.2　被一个-C 基团稳定的碳负离子 (Carbanions stabilized by one -C group) 64
4.1.3　形成碳负离子常用的碱(Commonly used bases for forming carbanion) 65
4.2　碳负离子的烷基化反应(Alkylation of carbanion) 65
4.2.1　活泼亚甲基化合物的烷基化(Alkylation of active methylene compound) 66
4.2.2　烷基化产物的水解 (Hydrolysis of the alkylated product) 69
4.2.3　单-C 基团稳定的碳负离子的烷基化(Alkylation of carbanion stabilized by one -C group) 70
4.2.4　间接法合成α-烷基醛和酮(Indirect synthesis of α-alkylated aldehyde and ketone) 72
4.3　碳负离子的酰基化反应(Acylation of carbanion) 74
4.3.1　活泼亚甲基化合物的酰基化(Acylation of active methylene compound) 74
4.3.2　单-C 基团稳定的碳负离子的酰基化(Acylation of carbanion stabilized by one -C group) 76
4.4　碳负离子的缩合反应(Condensation reaction of carbanion) 78
4.4.1　活泼亚甲基化合物的缩合反应(Condensation reaction of active methylene compound) 78
4.4.2　与α,β-不饱和体系发生迈克尔反应(Micheal reaction with α,β-unsaturated system) 81
4.4.3　单-C 基团稳定的碳负离子的缩合反应(Condensation reaction of carbanion tabilized by one -C group) 82
4.5　被磷或硫稳定的碳负离子(Carbanion stabilized by phosphorus or sulfur) 87
4.5.1　磷叶立德与维蒂希反应(Phosphorus ylide and Wittig reaction) 87
4.5.2　硫叶立德(Sulfur ylide) 90

第5章　有机合成中的氧化反应(Oxidation reactions in organic synthesis) 99
5.1　有机氧化基础知识(Basic knowledge of organic oxidation reaction) 99
5.2　无机氧化剂(Inorganic oxidant) 100
5.2.1　铬氧化剂(Chromium oxidant) 100
5.2.2　锰氧化剂(Manganese oxidant) 104
5.2.3　四氧化锇(OsO4) 105
5.2.4　高碘酸 (Periodic acid) 106
5.2.5　四乙酸铅[Pb(OAc)4] 106
5.2.6　臭氧(Ozone) 107
5.2.7　二氧化硒(SeO2 ) 108
5.2.8　卤素(Halogen) 109
5.3　有机氧化剂 (Organic oxidant) 110
5.3.1　过氧酸(Peroxy acid) 110
5.3.2　二甲基亚砜 (Dimethyl sulfoxide) 114
5.3.3　奥彭瑙尔反应(Oppenauer reaction) 115
5.3.4　坎尼扎罗反应(Cannizzaro reaction) 116

第6章　有机合成中的还原反应(Reduction reactions in organic synthesis) 122
6.1　有机还原反应的类型(Types of organic reduction reactions) 122
6.1.1　催化氢化 (Catalytic hydrogenation) 123
6.1.2　金属氢化物还原 (Metal hydride reduction) 126
6.1.3　电子转移反应(Electron transfer reaction) 128
6.2　常见官能团的还原(Reduction of common functional groups) 129
6.2.1　烯烃的还原(Reduction of alkene) 129
6.2.2　炔烃的还原(Reduction of alkyne) 130
6.2.3　醛和酮的还原(Reduction of aldehyde and ketone) 130
6.2.4　羧酸及其衍生物的还原(Redaction of carboxylic acids and their derivatives) 135
6.2.5　腈的还原(Reduction of nitrile) 136
6.2.6　亚胺的还原 (Reduction of imine) 136
6.3　碳-杂原子键的还原断裂(Reductive cleavage of carbon-heteroatom bond) 137

第7章　有机合成中的环化反应(Cyclization reactions in organic synthesis) 143
7.1　环化概述与策略(Introduction and strategy of cyclization reaction) 143
7.2　非环前体的环化反应(Cyclization reaction of non-cyclic precursor) 145
7.2.1　环的大小与反应速率(Ring size and reaction rate) 145
7.2.2　Baldwin 规则(Baldwin rules) 145
7.2.3　阴离子环化反应(Anionic cyclization reaction) 149
7.2.4　阳离子环化反应(Cationic cyclization reaction) 150
7.2.5　自由基环化反应(Free radical cyclization reaction) 152
7.3　双边环化与环加成反应(Bilateral cyclization and cycloaddition reaction) 152
7.3.1　六元环的形成(Formation of six-membered ring) 153
7.3.2　五元环的形成(Formation of five-membered ring) 158
7.3.3　四元环的形成(Formation of four-membered ring) 161
7.3.4　三元环的形成(Formation of three-membered ring) 162
7.3.5　中环和大环的形成(Formation of middle and big rings) 164
7.4　芳香族杂环的合成(Synthesis of aromatic heterocycle) 165
7.4.1　五元杂环的合成(Synthesis of five-membered heterocycle) 165
7.4.2　六元杂环的合成(Synthesis of six-membered heterocycle) 169
7.4.3　六元稠杂环化合物的合成(Synthesis of six-membered fused heterocyclic compound) 171

第8章　有机合成中的保护基(Protecting groups in organic synthesis) 178
8.1　保护基的基础知识(Basic knowledge of protecting groups) 178
8.2　羟基的保护(Protection of hydroxyl group) 179
8.2.1　生成醚来保护羟基(Protecting hydroxyl group by forming ether) 179
8.2.2　生成酯来保护羟基(Protecting hydroxyl group by forming ester) 182
8.3　羧基的保护(Protection of carboxyl group) 183
8.3.1　 生成酯来保护羧基(Protecting carboxyl group by forming ester) 184
8.3.2　生成原酸酯来保护羧基(Protecting carboxyl group by forming ortho ester) 186
8.4　羰基的保护(Protection of carbonyl group) 187
8.4.1　O,O-缩醛( 酮) 保护基(Protecting groups of O,O-acetal or O,O-ketal) 187
8.4.2　S， S-缩醛( 酮) 保护基(Protecting groups of S， S-acetal or S， S-ketal) 189
8.5　1,2-和1,3-二醇的保护(Protection of 1,2-and 1,3-diol) 191
8.6　氨基的保护(Protection of amino group) 192
8.6.1　叔丁氧羰基(t-Butyloxycarbonyl) 194
8.6.2　苄氧羰基(Carbobenzyloxy) 194
8.6.3　9-芴甲氧基羰基(9-Fluorenylmethyloxycarbonyl) 195

第9章　有机合成中的芳香环取代反应(Aromatic substitution reaction in organic synthesis) 201
9.1　亲电芳香取代(Electrophilic aromatic substitution) 202
9.1.1　傅-克烷基化(Friedel-Crafts alkylation) 202
9.1.2　傅-克酰基化(Friedel-Crafts acylation) 206
9.1.3　其他烷基化和酰化反应(Other alkylation and acylation reactions) 208
9.1.4　卤化(Halogenation) 209
9.1.5　硝化(Nitration) 212
9.2　亲核芳香取代(Nucleophilic aromatic substitution) 216
9.2.1　芳基重氮离子中间体的还原脱氮(Reductive denitrification of aryldiazonium ion intermediate) 217
9.2.2　由芳基重氮离子中间体合成苯酚(Phenol from aryldiazonium ion intermediate) 217
9.2.3　由芳基重氮离子中间体合成芳基卤化物(Aryl halide from aryldiazonium ion intermediate) 218

第10章　切断法(Disconnection approach) 224
10.1　单官能团醇的C—C 键的切断(C—C disconnection of monofunctional alcohol) 225
10.1.1　C—C 键的1,1-切断合成醇(1,1-C—C disconnection: the synthesis of alcohol) 226
10.1.2　C—C 键的1,2-切断合成醇(1,2-C—C disconnection: the synthesis of alcohol) 227
10.1.3　醇和相关化合物的合成实例(Example of the synthesis of alcohol and related compound) 227
10.2　单官能团羰基化合物C— C 键的切断(C— C bond disconnection of monofu-nctional carbonyl compound) 229
10.2.1　碳负离子的酰基化制备羰基化合物（Preparation of carbonyl compound by acylation of carbanion） 230
10.2.2　碳负离子的烷基化(Alkylation of carbanion) 232
10.2.3　炔烃的氧化(Oxidation of alkyne) 234
10.3　单官能团化合物的C=C 键的切断(C=C bond disconnection of monofunc-tional compound) 235
10.3.1　消除反应(Elimination reaction) 235
10.3.2　Wittig 反应(Wittig reaction) 237
10.3.3　炔烃的还原(Reduction of alkyne) 238
10.4　1,2-双官能团化合物的切断(Disconnection of 1,2-difunctional compound) 239
10.4.1　酰基负离子等价物(Acyl anion equivalent) 239
10.4.2　烯烃制备1,2-双官能团化合物(Preparation of 1,2-difunctional compound by alkene) 241
10.5　1,3-双官能团化合物的切断(Disconnection of 1,3-difunctional compound) 242
10.5.1　β-羟基羰基化合物的合成(Synthesis of β-hydroxy carbonyl compound) 242
10.5.2　α,β-不饱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-双官能团化合物的切断(Disconnection of 1,4-difunctional compound) 247
10.6.1　α-卤代酮作反常极性合成子制备1,4-双官能团化合物(Synthesis of 1,4-difunctional compound by using α-haloketone as unnatural polarity synthon) 248
10.6.2　酰基阴离子等价物的共轭加成(Conjugate addition of acyl anion equivalent) 249
10.6.3　4-羟基酮化合物切断为环氧化合物(Disconnection of 4-hydroxyketone into epoxid) 249
10.7　1,5-双官能团化合物的切断(Disconnection of 1,5-difunctional compound) 250
10.7.1　特定碳负离子等价物的Michael 加成(Micheal addition of specific carbanion equivalent) 250
10.7.2　罗宾逊环化反应(Robinson annelation) 253
10.7.3　1,5-二羰基化合物制备杂环(Synthesis of heterocycle by 1,5-dicarbonyl compound) 254
10.8　1,6-二羰基化合物的切断(Disconnection of 1,6-dicarbonyl compound) 254
10.8.1　环己烯氧化(Oxidation of cyclohexene) 255
10.8.2　Diels-Alder 反应(Diels-Alder reaction) 255
10.8.3　 Baeyer-Villiger 反应(Baeyer-Villiger reaction) 256
10.9　芳香族化合物的切断(Disconnection of aromatic compound) 257

第11章　不对称合成(Asymmetric synthesis) 264
11.1　基础知识与分析方法（Basic knowledge and analytical method） 264
11.1.1　手性（Chirality） 264
11.1.2　不对称合成中的一些术语（Terms in asymmetric synthesis） 267
11.1.3　对映体组成的测定（Determination of enantiomeric composition） 269
11.2　获得手性化合物的策略（Strategies for obtaining chiral compound） 271
11.3　**代方法：使用手性底物（First generation method: using chiral substrate） 272
11.4　第二代方法：采用手性助剂（Second generation method: using chiral auxiliary） 274
11.5　第三代方法：采用手性试剂（Third generation method: using chiral reagent） 275
11.6　第四代方法: 不对称催化（Fourth generation method: asymmetric catalysis） 276
11.6.1　金属催化剂（Metal catalyst） 277
11.6.2　酶催化剂（Enzyme catalyst） 282
11.6.3　有机小分子催化剂（Organic small molecule catalyst） 283