Errata for AWRORM, 2nd Ed.

The Art of Writing Reasonable Organic Reaction Mechanisms

Errata for the Second Edition

Any textbook is bound to have a few errors, and AWRORM is no exception. If you find any errors, please e-mail me and let me know. Thanks!

Enamine mechanism (p. 61)

An extra CO₂Et group magically appears in the final mechanism on p. 61, second line, second structure. It then disappears in the next structure. The mechanism should read as follows:

Thanks to Guido Kramp for spotting this error.

Syn or anti aldols (p. 63)

The penultimate sentence of the first paragraph on p. 63 should begin, "(Whether an aldol product is syn or anti....)" Thanks to David Flanagan for spotting this error.

DMAP catalysis (p. 71)

Apparently, contrary to common opinion, DMAP does not catalyze the acylation of nucleophiles with acyl halides. However, DMAP does catalyze the acylation of nucleophiles with acyl anhydrides and certain other activated esters by the mechanism indicated. The counterion (specifically, its basicity) is important because proton transfer is the rate-determining step in these acylations. A short discussion and references to earlier literature can be found in A. C. Spivey and S. Arseniyadis, Angew. Chem. Int. Ed. 2004, 43, 5436. Thanks to Prof. Edwin Vedejs for pointing out the error.

"Substituent" misspelled (p. 89)

In the third line of the third paragraph on p. 89, the word "substituent" is misspelled. Thanks to Feng Ni for spotting this error.

Iminium ion formation under acidic conditions (p. 138)

Formaldehyde is probably insufficiently basic (pK_a ca. –5) to be protonated by a simple ammonium salt (pK_a ca. 10). In the absence of a slight excess of free acid, the reaction of a ketone or aldehyde with an ammonium salt to give an iminium ion probably proceeds by the basic mechanism, p. 61, with solvent acting to deprotonate the ammonium ion initially. Thanks to Prof. Edwin Vedejs for pointing out this error.

Orbitals with zero coefficients (p. 156)

In the second and third full sentences on p. 156, ψ₃ and ψ₄ should be changed to ψ₂ and ψ₃. Thanks to David Weber for spotting this error.

Compound name (p. 160)

In the second paragraph on p. 160, "diphenylacetic acid" should be changed to "methyl phenylacetate". Thanks to David Weber for spotting this error.

Pentavalent N in nitrile oxide mechanism (p. 177)

The third structure in the mechanism towards the bottom of p. 177 contains a pentavalent N atom. The ⁺N=O should be ⁺N–O^–. Thanks to James Kirkham for spotting this error.

Oxy-Cope rearrangement (p. 208)

In the last line of graphics on p. 208, the OH group should be pseudoaxial, not pseudoequatorial, in the second structure, as shown:

Thanks to Matthew Campbell for spotting this error.

Cyclononatetraene cyclizations (p. 217)

all-cis-1,3,5,7-Cyclononatetraene can theoretically undergo four different electrocyclic ring closures, not just three.

Using single-electron arrows to show electron transfer (p. 237)

Although I have not seen single-electron curved arrows (fishhooks) used to indicate a one-electron transfer reaction, Prof. Edwin Vedejs tells me that he has seen it, so feel free to use it.

Initiation (p. 247)

The word "Initiation:" should follow the first line of structures in the Example on p. 247. Thanks to Hui Wang for spotting this error.

Acyloin condensations (p. 259)

In both Examples on p. 259, the reagents above the arrow on the first line of graphics should read "4 Na", not "2 Na". Thanks to Matthew Campbell for spotting this error.

Number of valence atomic orbitals (p. 272)

The second sentence on p. 272 should read, "Transition metals, by contrast, have nine valence AOs ...." Thanks to Hui Wang for spotting this error.

Alkyne hydration mechanism (p. 296)

In the catalytic cycle for alkyne hydration on p. 296, in the upper right structure, the two arrows should lead to and away from the opposite C atoms in the alkyne.