Book Review: Strategic Applications of Named Reactions in Organic Synthesis

It’s not often that a book redefines a genre, but Kürti & Czakó’s Strategic Applications of Named Reactions in Organic Synthesis (2005, Elsevier Academic Press) changes the landscape of named reaction books.  Without sounding too melodramatic, Strategic Applications will be the benchmark against which all future named reaction books will be judged – and they will all fail to live up to this new standard.  If you are an organic chemist, this book needs to be on your must buy list by the end of the day (have I hyped the book enough?)

Unlike The Periodic Table, Strategic Applications will not be a book you sit and read cover to cover.  Rather, Strategic Applications is an essential desktop reference in planning a synthetic route.  The most noticeable feature of the book upon first glance is the incredible breadth of detail given to each named reaction.  Each named reaction is given two complete (large) pages.  No more, no less.  The commentary begins with an Importance section giving a brief historical context as well as a general substrate scope and limitations.  As an example, the Suzuki Cross-Coupling begins:

In 1979, A. Suzuki and N. Miyaura reported the stereoselective synthesis of arylated (E)-alkenes by the reaction of 1-alkenylboranes with aryl halides in the presence of a palladium catalyst.  The palladium-catalyzed cross-coupling reaction between organoboron compounds and organic halides or triflates provides a powerful and general method for the formation of carbon-carbon bonds known as the Suzuki cross-coupling.  There are several advantages to this method: 1) mild reaction conditions; 2) commercial availability of many boronic acids; 3) the inorganic by-products are easily removed from the reaction mixture, making the reaction suitable for industrial processes; 4) boronic acids are environmentally safer and much less toxic than organo stannanes (see Stille coupling); 5) starting materials tolerate a wide variety of functional groups, and they are unaffected by water; 6) the coupling is generally stereo- and regioselective; and 7) sp3-hybridized alkyl boranes can also be coupled by the B-alkyl Suzuki-Miyaura cross-coupling.  some disadvantages are: 1) generally aryl halides react sluggishly; 2) by-products such as self-coupling products are formed because of solvent-dissolved oxygen; 3) coupling products of phosphine-bound aryls are often formed; and 4) since the reaction does not proceed in the absence of a base, side reactions such as racemization of optically active compounds or aldol condensations occur.

These introductions are followed by a general reaction scheme (click for larger):

Next is a detailed walk through of the detailed reaction mechanism.  As can be seen in the figure below, the most elegant aspect of this book is the careful use of color.  The reagents get their own colors, and new bonds formed are always black.  This is especially useful in reactions undergoing rearrangement, like the Ugi reaction:

The second page of each entry is dedicated to demonstrations of the title reaction in synthetic applications.  Several total syntheses are described with the step utilizing the named reaction highlighted.  I like this aspect.  It shows real-world applications and helps exemplify functional groups that tolerate the reaction conditions.

Each entry is extensively referenced, and even this is handled elegantly.  The references are split into three (sometimes four) categories: Seminal Publications, Reviews, Modifications and Improvements, and sometimes Theoretical Studies.  Several appendices at the back help your searching immensely.  The first lists all the named reactions in the book in chronological order of their discovery.  The next three appendices really help as they organize the reactions by reaction category (degradation, elimination, heterocycle formation…), reaction by affected functional group (from an alcohol, from a nitrile…), and reaction by target functional group (synthesis of epoxides, synthesis of oximes…)

This book is useful in many situations.  The other day the name of the Cannizaro reaction escaped me.  I couldn’t remember what it was called.  So I used the appendix for reaction by target functional group and looked up synthesis of carboxylic acids, and there it was!  I was writing a research proposal, and needed information on the Darzens glycidic ester condensation.  Thanks to the organization of the book, I was immediately directed to 4 reviews on the subject.  In my research, I was (am) having trouble with a directed ortho metalation reaction.  Forty reaction references appeared at my fingertips directing me to more information on the subject.  It’s also fun to browse through reactions I’ve never ever heard of (like the Hunsdiecker or Minisci Reactions).

I cannot stress enough how detailed and thorough and indispensable Strategic Applications is to the synthetic organic chemist.  When your book has a foreword by E. J. Corey and an introduction by K. C. Nicolaou, you know you’ve run into a winner.  Without question, this is the best named reaction book around.

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Survivor: Mechanisms (now accepting logo submissions)

I read an interesting article in May’s issue of J. Chem. Ed. titled “Can Reaction Mechanisms Be Proven?” by Allen Buskirk and Hediyeh Baradaran of BYU.  Intriguing.  So I pop open the pdf and a Note from the Editor is boxed at the top of the page before the article starts.  It says:

“Can Reaction Mechanisms Be Proven?” generated spirited responses from its reviewers. The reviews were approximately evenly divided, and all were of very high quality. The authors agreed with the editor’s proposal that the reviewers convert their reviews into rebuttals or affirmations of the authors’ position for publication along with the article, which has been revised based on the reviews. Most agreed to such a process and their comments appear here. We hope that publication of this paper and well-reasoned rebuttals such as those provided here will initiate a wide-ranging discussion. JCE will provide an online forum for further discussion of the issue. Our hope is that both faculty and students will contribute their opinions and ideas to this discussion. -JWM

Huh.  You don’t usually hear about that happening too often.  So now I had to read the article.  It’s pretty fascinating, and I encourage you to read it all.  I’ll summarize and give my thoughts below the jump

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