Preface

A PREVIEW OF THE FIFTH EDITION

I believe, and research in chemical education shows, that students who make the effort to learn

but still have trouble in organic chemistry are in many cases trying to memorize their way
though the subject. One of the keys to students' success, then, is to provide them with help in
relating one part of the subject to the next-to help them see how various reactions that seem
very different are tied together by certain fundamentals. An overarching goal of my text is to
help students achieve a relational understanding of organic chemistry. Here are some of the
ways that I have tried to help students meet this goal.

use of an Acid-Base Framework ts a Key to Understanding

Mechanisms
Although I have organized Organic Chemistry Sth Edition by functional group, I have used
mechanistic reasoning to help students understand the "why" of reactions. Mechanisms alone,
however, do not provide the relational understanding that students need. Left to their own devices, many students view mechanisms as something else to memorize, and they are baffled

I believe passionately that an understanding of acid-base

chemistry is the key that can unlock the door to a mechanistic understanding of much organic
chemistry. In Organic Chemistry 5th Edition,I use both Lewis acids and bases and Brpnsted
acids and bases as the foundations for mechanistic reasoning. Although students have memorized the appropriate definitions in general chemistry, few have developed real insight about
the implications of these concepts for a broader range of chemistry. I have dedicated Chapter 3
to these fundamental acid-base concepts. The terms "nucleophile," "electrophile," and "leaving group" then spring easily from Lewis and Br6nsted acid-base concepts, and the curvedarrow notation makes sense. I have provided a substantial number of drill problems to test how
well students have mastered these principles. I have reinforced these ideas repeatedly with
each new reaction type. Free-radical reactions are also covered, but not until the electron-pair
by the "curyed-arrow" notation.

concepts are fully established.

Tiered Topic Development Provides Reinforcement of

lmportant ldeas
I have introduced complex subjects in "tiers." This means that students will see many concepts
introduced initially in a fairly simply way, then reviewed with another layer of complexity
added, and reviewed again at a greater level of sophistication.
Acid-base chemistry discussed above, is an example of tiered development. After the initial chapter on acid-base chemistry and the curved-arrow notation, these concepts are revisited in detail as they are used in the early examples of reactions and mechanisms, and again
with the introduction of each new reaction type.

XXXI

XXX|i

PREFACE

The presentation of stereochemistry is another example. The basic idea of stereoisomers is

introduced in Chapter 4 (Alkenes). A full chapter on stereochemistry comes two chapters
later. Cyclic compounds and the stereochemistry of reactions follow subsequently. Then the
ideas of group equivalence and nonequivalence are introduced even later, both in the context
of enzyme catalysis and NMR spectroscopy.
The approach to organic synthesis is yet another example. I start with simple reactions and
then show students how to think about them in reverse. Then, later, I introduce the idea of multistep synthesis using relatively simple two- and three-step sequences. Later still, we have another discussion in which stereochemistry comes into play. Even later, the use of protecting
groups is introduced.
This "tiered presentation" of key topics requires some repetition. Although the repetition of
key points might be considered inefficient, I believe that it is crucial to the learning process.
When a topic is considered after its first introduction, I have provided detailed cross-referencing to the original material. Students are never cast adrift with terminology that has not been
completely defined and reinforced.

Everyday Analogies Help Students to Gonstruct Their Own

Knowledge
I believe in the constructivist theory of learning, which holds that students construct learning
in their own minds by relating each new idea to something they already know. This is why the
relational approach to learning organic chemistry is so important. For the same reason, I have
provided common analogies from everyday experience for many of the discussions of chemical principles so that students can relate a new idea to something they already know. One of
many examples can be found in the sidebar on p. 164.

Biological Examples Motivate Students Interested in the Allied

Health Sciences
Many organic chemistry classes are populated largely by premedical students, prepharmacy
students, and other students interested in the life sciences. Biological examples help to motivate these students. I have provided a number of examples from modern biochemistry and
medicine throughout the book. Amino acids and proteins have a dedicated chapter that has
been completely rewritten in light of modern developments. Carbohydrates also have a dedicated chapter that has been moved so that it now follows carbonyl and amine chemistry. I have
integrated many other biological examples into discussions of the relevant chemistry. The ultimate goal of these examples is to reinforce the chemistry being discussed with material that
students should find particularly relevant. Among these are discussions of cell membranes,
bioorganic stereochemistry, pheromones, imaging agents, nucleic acids, coenzyme mechanisms, and many, many more. One of many such discussions, for example, is found in the
sidebar on pp. 396-398 and the accompanying illustration on p. 399.

Students in an Introductory course should see Examples of

Contemporary Organic Chemistry
The "canon" ofundergraduate organic chemistry necessarily contains many classical reactions,
but this text introduces some very modern chemistry as well. For example, the 4th edition introduced a section on transition-metal catalysis, a field that has literally exploded in the last few
years. This section carefully explains the conventions used in the field for electron counting and
calculating oxidation states. This edition builds on that introduction, which previously included

PREFACE XXXIII
the Heck and Stille reactions, by adding sections on the Suzuki coupling, alkene metathesis,
and Buchwald-Hartwig amination. Asymmetric epoxidation is also introduced, and a modern
approach to understanding the rate accelerations observed for many intramolecular reactions
has been developed. There is a somewhat higher level of molecular orbital theory than in previous editions. Accompanied by detailed explanations and illustrations, MO theory is related to
practical considerations, such as the meaning of resonance structures, the basis of aromaticity,
and the understanding of reaction stereochemistry.

solvint Problems ls an Essential component of the Learning

Process
We all know that solving problems is a key to learning organic chemistry. I have provided
1672 problems, many of them multipart, ranging from drill problems to problems that will
challenge the most astute students. Many are based directly on material in the literature. The
840 problems within the body of the text are typically drill problems that test whether students
understand the current material. The 832 problems at the end of the chapters cover material
from the entire chapter and, in many cases, integrate material from earlier chapters.
Additionally, I have interspersed 123 Study Problems throughout the text. Each of these
problems has a worked-out solution that carefully shows students the logic involved in the
problem-solving process.
Many students rely too heavily on the Solutions Manual. To help avoid this problem, I have
reintroduced in this edition a "paired problems" approach. This means that the solutions to
about6OVo of the problems are provided inthe Study Guide and Solutions Manual that accompanies the text (see below), but the solutions to the rest of the problems are not provided to the
students. Instructors will receive complete solutions to these "unsolved" problems in PDF format. An instructor who would like to make these solutions available to his or her students can
simply post them on a course Web site or hand them out. I have experimented with different
ways to use these additional solutions. For example, I have provided the relevant solutions to
students just prior to major exams; this strategy encourages them to try these problems without immediate help from the solutions manual, but also allows them to check their answers
later. Alternatively, an instructor could these additional problems as the basis for exam questions. Many of the "unsolved" problems are adjacent to at least one "solved" problem of the
same type.

A Full-Golor Presentation lmproves Pedagogy

With this edition, this textbook makes its first appearance in full color. As I have redesigned
the art program to make use of color, I have kept a few things uppermost in my mind: color
should be used solely for functional, pedagogical purposes; and both gratuitous illustrations
and excessive color should be avoided. (I believe students have enough to worry about rather
than trying to figure out what's important in a textbook.) The use of color, the presentation of
the art, and the text design itself flow from the ideas in The Psychology of Everyday Things, a
book by Don Norman. The core idea is that these elements in the text should provide subliminal cues to students that facilitate the learning process.

Supplements Provide Additional Help for eoth Students and

Instructors

l.

The Study Guide and Solutions Manual presents chapter summaries, glossaries of terms,

reaction summaries, solutions to selected problems, Study Guide Links, and Further

XXXIV

PREFACE

Explorations. The Study Guide Links, which are called out with margin icons in the text,
are additional discussions of certain topics with which, in my experience, many students
require additional assistance. Examples are "How to Study Organic Reactions," and
"Solving Stmcture Problems." The Further Explorations, also called out with margin
icons in the text, are short discussions that move beyond the text material. An example
is "Fourier-Transform NMR."
2. Molecular models (Model 1013) from Maruzen International are available as a bundle
with the textbook. For more information and pricing, please contact Ben Roberts:
bwr@ roberts-publishers.com.

will provide, to adopting instructors, a PDF image of the problem solutions that are
not provided in the Study Guide and Solutions Manual (see the discussion of "paired
problems" above), as well as full-color images of all figures in conventional formats so
that they can be used in classroom presentations. Instructors at adopting institutions who
want this material should request it from the publisher at bwr@roberts-publishers.com.
4. As with the fourth edition, we will maintain, on the World-Wide Web, an up-to-date list
of errata in PDF format for both the text and the Study Guide and Solutions Manual supplement. These lists of errors will be generally available to instructors and students
3. We

alike.

A BOOK WITH A SCHOIARIY HISTORY

The first edition of Organic Chemistry, published in 1984, required 7)years of development,
because each topic was researched back to the original or review literature. Subsequent editions, including this one, have continued this scholarly development process. Almost every reaction example is taken from the literature. Each edition has benefited from a thorough peer
review.

ACKNOWLEDGMENTS
I am indebted to my dean, Craig Svensson, and my department head, Rick Borch, for providing a sabbatical leave in 2007-2008, as well as a climate in which this edition could be completed successfully. The electronic resources of the Purdue Library have streamlined the research process for this text in a way that was unimaginable 25 years ago, and I would like to
thank Emily Mobley, Purdue's Dean of Libraries Emerita, for bringing the electronic library
to fruition, and Jim Mullins, the present dean, for fostering its continued improvement.
Thanks to my faculty and staff colleagues at Purdue and beyond-John Grutzner, Don
Bergstrom, Mark Green, Chris Rochet, Ross Weathernan, Phil Fuchs, Mark Lipton, Ei-ichi
Negishi, Markus Lill, David Nichols, Mark Cushman, Arun Ghosh, John Bartmess (University of Tennessee), Bob Hammer (formerly of Louisiana State University), Karl Wood, David
Allen, and Susan Holladay-for advice, assistance, and suggestions. Special thanks go to two
very special teaching assistants, Lisa Bonner and Animesh Aditya, for their hard work, their
advice, and their effective and inspiring teaching. The reviewers named in the list that follows
this preface provided invaluable assistance in polishing this text. I am particularly indebted to
Prof. David Hansen of Amherst College, Prof. Paul Rablen of Swarthmore College, and Prof.
Carolyn Anderson of Calvin College, who provided invaluable suggestions through all or
most of the project. Prof. Ahamindra Jain of Harvard University, a dedicated teacher and a delightful collaborator, made some very valuable suggestions in the early going, and I was very
much lookins forward to workins with him as mv coauthor on the Studv Guide and Solutions

PREFACE

Manual supplement. Sadly, Ahamindra passed away in 2008, and is sorely missed. I would
also like to thank the many students from all over the country who made suggestions, offered
comments, and reported errors. I welcome correspondence with the students using this edition. I can be reached by e-mail at marc.loudon.l @purdue.edu.
My relationship with the professionals at Side By Side Studios in San Francisco, Mark Ong
and Susan Riley, has been particularly gratifying. Not only has their composition work been
superb, but also their advice has been invaluable. Side By Side gets five stars! Working with
Ben Roberts at Roberts and Company Publishers has also been a delight, and I hope our association continues far into the future. I very much appreciate the hard work, advice, and attention to detail of the copy editor, John Murdzek, and the proofreader, Gunder Hefta. I would
particularly like to thank those acknowledged separately in the Credits section for their willingness to allow me to reproduce their materials.
I could not have completed this project without the love and support of Judy and my family, for which I am grateful beyond words.
My wish is that the students who use this text will see the amazing diversity and beauty of
science through their study of organic chemisby, and that they will benefit from using this
book as much as I have enjoyed writing it.
October 2008
West Lafay ette, Indiana

Marc Loudon