In 1997, Volume 50 of Organic Reactions was published in a handsome and appropriate gold hard-cover edition. This was only the third volume in this prestigious series that consisted of a single chapter. The treatise, The Stille Reaction, describes a palladium-catalyzed cross-coupling between a carbon ligand on tin and a carbon with electrophilic character. This reaction has been around only since 1977, and the literature is covered here through 1994 with a few references in 1995. It is truly astounding that, in the space of about 17 years, a new reaction could generate enough literature for not only a chapter in Organic Reactions, but a complete volume of 652 pages, 864 literature citations, and more than 4300 specific reaction examples. The editorial board of Organic Reactions has graciously decided to make this extensive review available to a broader audience by authorizing a paperback edition of The Stille Reaction.

While the mechanistic details of the Stille reaction are generally understood, there are many fine points that must be tuned to each case. For instance, about 15 different solvents have been used, ranging in polarity from benzene to water; at least ten different ligands for the palladium atom are available and they range from hard to soft; CuI, Ag₂CO₃, and LiCl are sometimes useful cocatalysts but sometimes have no effect, and in some cases LiCl is inhibitory; vinyl triflates couple with alkenyl-, alkynyl- and allylstannanes but not with arylstannanes; reaction temperatures vary from room temperature to refluxing DMF. An important consideration is that most stannanes are reasonably air and moisture stable and do not react with most common functional groups. Thus, it is not necessary to build protection-deprotection sequences into the synthetic scheme.

The extensive reaction examples are arranged in 33 tables that show, for each reaction, the structures of the electrophile, the stannane, and the product and specify the catalyst, cocatalyst, solvent temperature, and yield. The tables are sequenced by the structure of the electrophiles, which are listed in order of increasing carbon count for the group that is transferred. For the same electrophile, different stannanes are listed by the increasing carbon count of the group transferred from tin. For example, the three tables with the most examples are titled "Direct Cross-Coupling of Alkenyl Electrophiles," "Direct Cross-Coupling of Aryl Electrophiles", and "Direct Cross-Coupling of Miscellaneous Heterocyclic Electrophiles". They include 661, 1043, and 339 examples, respectively.

The narrative section of the book begins with an overview of the mechanism, regiochemistry, and stereochemistry of the Stille reaction. This is followed by discussions of the scope and limitations of both the electrophilic species and the stannane. The Stille reaction can also involve the incorporation of a carbonyl in the coupling sequence. The carbonyl results from inclusion of carbon monoxide in the reaction medium. This variation of the reaction is also discussed. The narrative continues with discussion of Hech-Stille tandem sequences, side reactions, and comparisons with other cross-coupling reactions. It concludes with a very useful section on experimental considerations and nine examples of procedures from the literature. The book also includes a useful index (covering the narrative section), which has been added to the original Organic Reactions edition. Finally, it should be noted that a careful inspection of the thousands of structures in the table did not turn up one typographical error.

In a 1993 research paper (J. Org. Chem. 1993, 58, 5434) the lead author, Vittorio Farina, writes that "A survey of applications of transition metal-mediated cross-coupling reactions for the year 1992 shows that the Stille coupling accounts for over 50% of all cross-couplings reported." It seems that, given the magnitude of this review, the significance of this reaction has continued to grow. Every synthetic organic chemist should have easy access to the massive amount of information contained in this book.