Description
Students of chemistry are not hard-pressed to fi nd a text to support their learning in organic chemistry through their years at university. The shelves of a university bookshop will usually offer a choice of at least half a dozen—all entitled ‘Organic Chemistry’, all with substantially more than 1000 pages. Closer inspection of these titles quickly disappoints expectations of variety. Almost without exception, general organic chemistry texts have been written to accompany traditional American sophomore courses, with their rather precisely defi ned requirements. This has left the authors of these books little scope for reinvigorating their presentation of chemistry with new ideas.
We wanted to write a book whose structure grows from the development of ideas rather than being dictated by the sequential presentation of facts. We believe that students benefit most of all from a book which leads from familiar concepts to unfamiliar ones, not just encouraging them to know but to understand and to understand why. We were spurred on by the nature of the best modern university chemistry courses, which themselves follow this pattern: this is after all how science itself develops. We also knew that if we did this we could, from the start, relate the chemistry we were talking about to the two most important sorts of chemistry that exist—the chemistry that is known as life, and the chemistry as practised by chemists solving real problems in laboratories.
We aimed at an approach which would make sense to and appeal to today’s students. But all of this meant taking the axe to the roots of some long-standing textbook traditions. The best way to fi nd out how something works is to take it apart and put it back together again, so we started with the tools for expressing chemical ideas: structural diagrams and curly arrows. Organic chemistry is too huge a fi eld to learn even a small part by rote, but with these tools, students can soon make sense of chemistry which may be unfamiliar in detail by relating it to what they know and understand. By calling on curly arrows and ordering chemistry according to mechanism we allow ourselves to discuss mechanistically (and orbitally) simple reactions (addition to C=O, for example) before more complex and involved ones (such as SN1 and SN2).
Complexity follows in its own time, but we have deliberately omitted detailed discussion of obscure reactions of little value, or of variants of reactions which lie a simple step of mechanistic logic from our main story: some of these are explored in the problems associated with each chapter, which are available online.1 We have similarly aimed to avoid exhuming principles and rules (from those of Le Châtelier through Markovnikov, Saytseff, least motion, and the like) to explain things which are better understood in terms of unifying fundamental thermodynamic or mechanistic concepts.
Brief contents
Abbreviations xv
Preface to the second edition xvii
Organic chemistry and this book xix
1 What is organic chemistry? 1
2 Organic structures 15
3 Determining organic structures 43
4 Structure of molecules 80
5 Organic reactions 107
6 Nucleophilic addition to the carbonyl group 125
7 Delocalization and conjugation 141
8 Acidity, basicity, and pKa 163
9 Using organometallic reagents to make C–C bonds 182
10 Nucleophilic substitution at the carbonyl group 197
11 Nucleophilic substitution at C=O with loss of carbonyl oxygen 222
12 Equilibria, rates, and mechanisms 240
13 1H NMR: Proton nuclear magnetic resonance 269
14 Stereochemistry 302
15 Nucleophilic substitution at saturated carbon 328
16 Conformational analysis 360
17 Elimination reactions 382
18 Review of spectroscopic methods 407
19 Electrophilic addition to alkenes 427
20 Formation and reactions of enols and enolates 449
21 Electrophilic aromatic substitution 471
22 Conjugate addition and nucleophilic aromatic substitution 498
23 Chemoselectivity and protecting groups 528
24 Regioselectivity 562
25 Alkylation of enolates 584
26 Reactions of enolates with carbonyl compounds: the aldol and Claisen
reactions 614
27 Sulfur, silicon, and phosphorus in organic chemistry 656
28 Retrosynthetic analysis 694
29 Aromatic heterocycles 1: reactions 723
30 Aromatic heterocycles 2: synthesis 757
31 Saturated heterocycles and stereoelectronics 789
32 Stereoselectivity in cyclic molecules 825
33 Diastereoselectivity 852
34 Pericyclic reactions 1: cycloadditions 877
35 Pericyclic reactions 2: sigmatropic and electrocyclic reactions 909
36 Participation, rearrangement, and fragmentation 931
37 Radical reactions 970
38 Synthesis and reactions of carbenes 1003
39 Determining reaction mechanisms 1029
40 Organometallic chemistry 1069
41 Asymmetric synthesis 1102
42 Organic chemistry of life 1134
43 Organic chemistry today 1169