Advanced Organic Chemistry: Part A - Structure and Mechanisms

Citation

Carey, F. A., & Sundberg, R. J. (2007). Advanced Organic Chemistry. Part A: Structure and Mechanisms (5th ed.). Springer.

Chapter Summary

Part A of the fifth edition has twelve chapters in about 1,150 pages. The publisher describes the material as organised around fundamental structural topics (structure, stereochemistry, conformation and aromaticity) and basic mechanistic types: nucleophilic substitution, addition reactions, carbonyl chemistry, aromatic substitution and free radical reactions. It is the first of two volumes, to be used with Part B, Reaction and Synthesis. The book assumes completion of an introductory organic chemistry course, reviews the fundamental concepts for each topic, and gives extensive references to the primary and review literature.

Chapter 1: Chemical Bonding and Molecular Structure

The opening chapter (about 117 pages) deals with bonding and structure. Its contents include heteroatom hyperconjugation and the anomeric effect, the representation of electron density by the Laplacian function, bonding in cyclopropane and other small rings, and a density-functional (DFT) formulation of reactivity through the Fukui function, in keeping with the edition's emphasis on computational chemistry.

Chapter 2: Stereochemistry, Conformation, and Stereoselectivity

A chapter of some 130 pages that includes the analysis and separation of enantiomers, chiral shift reagents, enzymatic resolution and desymmetrization with lipases, esterases, proteases and acylases, the anomeric effect in cyclic compounds, and polar substituent effects in reduction.

Chapter 3: Structural Effects on Stability and Reactivity

The title places the chapter between the structural chapters and the mechanistic ones: it relates structural effects to stability and reactivity, a bridge between the two halves of the volume's organisation.

Chapter 4: Nucleophilic Substitution

The first chapter on a basic mechanistic type, about 85 pages.

Chapter 5: Polar Addition and Elimination Reactions

A 105-page chapter on polar addition and elimination.

Chapter 6: Carbanions and Other Carbon Nucleophiles

A shorter chapter (about 50 pages) on carbon nucleophiles.

Chapter 7: Addition, Condensation and Substitution Reactions of Carbonyl Compounds

The chapter on carbonyl chemistry, about 85 pages.

Chapter 8: Aromaticity

A chapter of about 58 pages, which includes a section on the criteria of aromaticity.

Chapter 9: Aromatic Substitution

About 60 pages on substitution reactions of aromatic compounds.

Chapter 10: Concerted Pericyclic Reactions

One of the longest chapters (about 130 pages); its contents include electrocyclic reactions, the Diels-Alder reaction and its enantioselective versions, and trienes.

Chapter 11: Free Radical Reactions

About 105 pages on radical reactions.

Chapter 12: Photochemistry

The final chapter, about 80 pages, closes the volume.

Key Concepts

Chapters 1–3

• Bonding and structure: electron-density, hyperconjugation and computational descriptions of bonds.
• Stereochemistry and conformation: stereoisomers, their analysis and separation, and stereoselectivity.
• Structure-reactivity relationships: how structure sets stability and reactivity.

Chapters 4–7

• Nucleophilic substitution, polar addition and elimination, carbon nucleophiles and carbonyl reactions: the basic polar mechanistic types.

Chapters 8–12

• Aromaticity and aromatic substitution: criteria of aromaticity and the substitution reactions of aromatic systems.
• Pericyclic reactions: concerted reactions such as electrocyclic and Diels-Alder reactions.
• Free radical reactions and photochemistry: the nonpolar and light-induced mechanisms at the end of the volume.

Critical Analysis

Strengths

• A mechanism-based organisation. The twelve chapters follow structural topics, then the basic mechanistic types, so a reader can look up a topic by what a reaction is.
• References to the literature. The publisher stresses extensive references to primary and review literature and examples of data and reactions that illustrate and document the generalisations, which suits readers learning to use the research literature.
• Updated for computation. The fifth edition adds material reflecting advances since 2001, especially in computational chemistry, and a companion website gives digital models for study of structure, reaction and selectivity.
• Fundamentals reviewed. The book reviews the fundamental concepts of each topic it treats, so it remains usable for readers whose introductory course was some time ago.
• Standing. The publisher describes it as having held its place since 1977 as a premier textbook in the field.

Limitations

• Size and density. At roughly 1,150 pages for Part A alone it is a reference more than a one-term text, and a course must choose chapters.
• Half of a pair. Synthesis and reactions in the preparative sense are in Part B; Part A has to be read with Part B for the full picture.
• Assumes introductory organic chemistry. The publisher states that completion of an introductory course is assumed, so it is not a first course.
• Dated in places. The edition is from 2007, and developments in computational and structural methods since then are not covered.
• Instructor-only solutions. Solutions to the exercises are provided to instructors online, so self-study readers have no published answers from the publisher.

Where It Fits in the Course

Among the course books, McMurry's Organic Chemistry and Clayden, Greeves and Warren's Organic Chemistry are full textbooks (McMurry's described as suited to the usual two-course sequence), and Klein's Organic Chemistry as a Second Language is a companion for first-semester practice; Patrick's Organic Chemistry: A Very Short Introduction is a brief overview. Carey and Sundberg come after all of these: they assume the sequence and move to a treatment organised for research use.

Anslyn and Dougherty's Modern Physical Organic Chemistry is the nearest peer: a graduate text on structures, energetics and mechanisms from a physical organic standpoint. Carey and Sundberg are broader in the reactions they survey and heavier in literature references, whereas Anslyn and Dougherty connect bonding, strain, stereochemistry and solvation with the experimental and computational methods used to establish mechanisms. The two are natural companions for an advanced course.

How to Use This Book

The book is aimed, according to the publisher, at advanced undergraduates and beginning graduate students in chemistry who need a foundation for the research literature of organic chemistry.

• Core for a course on structure and mechanism: Chapters 1 to 3, then Chapters 4 to 7 for the polar mechanisms.
• Selective: Chapters 8 to 12 can be picked by interest: aromatic chemistry (8 and 9), pericyclic reactions (10), radicals (11) or photochemistry (12).
• As a reference: go to the chapter on the mechanism type you are studying and follow its references to original papers.
• Pairing: use Part B alongside it when the course turns to synthesis, and use the companion website's digital models for structure and reactivity.