The Art of Writing Reasonable Organic Reaction Mechanisms

Errata for the Third 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!

Errors in textbook

PageDescription
13Type of orbital
23–24Arrow heads
44Position of nucleophilic C
47Formula of CAN
56Missing C
72Order of energy of carbonyl compounds backward
88Misplaced electron-flow arrow
98Description of product
130Stereochemistry of product
161Mechanism of diazonium ion formation from amine and HNO2
169Misnamed reaction
187Missing O
206Description of 3-membered ring intermediate
237PhN → X
238Double bond to H
247Relationship of equilibrium constant to kinetic and thermodynamic stabilities
254Whether H(s) or ψ1 is lower in energy
255–256Wrong R group numbers
258Missing C in formula
274Position of third line of graphics
276Too many π bonds
279Wrong reagent
284Order of energy of alkyl radicals backward
285Missing plus sign
290Wrong kind of arrows; O electron count in ketyl radical
299Numbering of R groups in transition state structure
360Reaction of Zr compound with CuX
374Wrong Ti compound
386Oxidation state of [LnPdX](−)
390Missing P
401n-Bu should be Ph
417Ketone, not alcohol

Errors in answer keys

PageDescription
Chap. 1 end-of-chapter question 2gLess acidic compound circled
Chap. 4 end-of-chapter question 6vNumber of electrons in electrocyclic reaction
Chap. 5 end-of-chapter question 3eeOmitted answer to question 3ee
Chap. 6 in-chapter question 6.11Cl not Br
Chap. 6 end-of-chapter question 1bOxidation state of allyl–Pd complexes


Type of orbital (p. 13)

In the figure on the bottom, the orbital on the left should be described as an sp3 orbital, not an sp2 orbital. Thanks to Michael W. Fennie for reporting this error.


Arrow heads (pp. 23–34)

The curved lines should not have arrow heads at the beginning or end. Thanks to Tadashi Okuyama for reporting this error.


Position of nucleophilic C (p. 44)

The nucleophilic C is on the bottom of both starting material and product, not on the right. Thanks to Tadashi Okuyama for reporting this error.


Formula of CAN (p. 47)

CAN is an abbreviation for Ce(NH4)2(NO3)6, not Ce(NH3)2(NO3)6. Thanks to Shen Muzhi for reporting this error.


Missing C (p. 56)

In question 4c, a C atom is missing from the product. The correct figure is below. Thanks to Kaitlyn Corazzata for reporting this error.


Order of energy of carbonyl compounds backward (p. 72)

The order of energy of the different carbonyl compounds is stated backward in the text. The correct order is RCOCl (highest in energy) > RCO2COR > RCHO > R2CO > RCO2R > RCONR2 (lowest in energy). The associated figure is correct. Thanks to Tom Dawson for reporting this error.


Misplaced electron-flow arrow (p. 88)

In the second step of the mechanism of the serine proteases, the electron-flow arrow showing the formation of the new N–H bond should originate at the cleaving C–N bond, as shown below. Thanks to Alex Lin for reporting this error.


Description of product (p. 98)

In the last line of p. 98, "carbanionic" should be "organolithium". Thanks to Tadashi Okuyama for reporting this error.


Stereochemistry of product (p. 130)

In question gg, the product should be trans, not cis. Thanks to an unnamed reader for reporting this error.


Mechanism of diazonium ion formation from amine and HNO2 (p. 161)

The mechanism for the reaction of a primary amine with HNO2 that is shown and discussed in the text is probably incorrect. The initial protonation of HNO2 should occur at the O doubly bonded to N, not the O singly bound to N, as shown here.


Misnamed reaction (p. 169)

The reaction in Problem 3.17 is a Strecker reaction, not a Stetter reaction. Thanks to Michael W. Fennie for reporting this error.


Missing O (p. 187)

The product in problem (i) is missing an O atom. The correct equation is below. Thanks to Feiyu Zhou for reporting this error.


Description of 3-membered ring intermediate (p. 206)

On p. 206, in the fourth line of text after the first figure, the text describes the 3-membered ring intermediate in Mechanism 1 as a cyclopropane, but it is better described as a cyclopropanone. Thanks to Tadashi Okuyama for reporting this error.


PhN → X (p. 237)

In the first figure on page 237, the two PhN atom labels in the products should be X. Thanks to Tadashi Okuyama for reporting this error.


Double bond to H (p. 238)

The bottom right structure in the figure in the middle of the page should show a single bond, not a double bond, to H. Thanks to Tadashi Okuyama for reporting this error.


Relationship of equilibrium constant to kinetic and thermodynamic stabilities (p. 247)

The second sentence in section 4.4.1 asserts that the position of the equilibrium in sigmatropic rearrangements depends on both the thermodynamic and kinetic stabilities of the starting material and product. In fact, only the thermodynamic stabilities are relevant. Thanks to Tadashi Okuyama for reporting this error.


Whether H(1s) or ψ1 is lower in energy (p. 254)

In the second paragraph on page 254, the seventh sentence should read as follows:

It is clear that the H(1s) orbital is lower in energy than the antibonding orbital ψ1, but it is not clear whether H(1s) or ψ0 [not ψ1] is lower in energy.
Thanks to You-Chen Lin for reporting this error.


Wrong R group numbers (p. 255–256)

In the last figure on p. 255 and the first figure on p. 256, the two R groups on the right side of the transition-state structure should be R3 and R4, not R1 and R2. Thanks to You-Chen Lin for reporting this error.


Missing C in formula (p. 258)

In the last figure on p. 258, the reagent above the arrow should be CH3C(OEt)3. Thanks to Adam Kang for reporting this error.


Position of third line of graphics (p. 274)

The third line of graphics on p. 274 should be below the paragraph beginning with the number 5, not above it. Thanks to Tadashi Okuyama for reporting this error.


Too many π bonds (p. 276)

In question (i), the first structure should have only one double bond in the ring, as shown below. Thanks to You-Chen Lin for reporting this error.


Wrong reagent (p. 279)

In question (u), the reagent above the arrow should be (COCl)2, not COCl2. Thanks to Tim Chyrklund for reporting this error.


Order of energy of alkyl radicals backward (p. 284)

The order of energy of alkyl radicals is stated backward in the text. The correct order of energy is 3° (lowest in energy) < 2° < 1° < ·CH3 (highest in energy). Thanks to Michael W. Fennie for reporting this error.


Missing plus sign (p. 285)

A plus sign is missing from the leftmost N atom in the first structure in the second line of structures on p. 285. Thanks to Shuqi Ye for reporting this error.


Wrong kind of arrows; O electron count in ketyl radical (p. 290)

In the first figure, the two resonance arrows on the right should be replaced with regular reaction arrows.

In the second figure, the O atom of the ketyl radical (second figure) should bear six unshared electrons, not five. The correct figure is below. Thanks to Michael W. Fennie for reporting this error.


Numbering of R groups in transition state structure (p. 299)

The R1 and R2 groups on the right side of the transition state structure in the first line of graphics on p. 299 should be R3 and R4. Thanks to Tadashi Okuyama for reporting this error.


Reaction of Zr compound with CuX (p. 360)

In the second figure, the reaction of the Zr compound in the center with Cu–X to the lower right should be labelled as a transmetallation (c), not as an insertion (b). Thanks to You-Chen Lin for reporting this error.


Wrong Ti compound (p. 374)

In the second paragraph on page 374, line 3, Cp2TiCl2 should be replaced with Ti(O-i-Pr)4. Thanks to Tadashi Okuyama for reporting this error.


Oxidation state of [LnPdX](−) (p. 386)

The Pd atom in LnPdX, the compound on the bottom left in the first figure, is in the oxidation state (0), not (II). Thanks to You-Chen Lin for reporting this error.


Missing P (p. 390)

In the last equation on p. 390, the reagent on the arrow should be (Ph3P)4Pd, not (Ph3)4Pd. Thanks to Tadashi Okuyama for reporting this error.


n-Bu should be Ph (p. 401)

In the last equation on p. 401, the n-Bu group should be a Ph group. Thanks to Tadashi Okuyama for reporting this error.


Ketone, not alcohol (p. 417)

Structure 6 in question 3(d) should be a ketone, not an alcohol. The correct figure is below. Thanks to Michael W. Fennie for reporting this error.


Less acidic compound circled (answer key Chap. 1 end-of-chapter question 2g)

The text correctly describes the more acidic compound, but the less acidic compound is circled. Thanks to Terence Ma for reporting this error.


Number of electrons in electrocyclic reaction (answer key Chap. 4 end-of-chapter question 6v)

The text incorrectly describes the first step of the mechanism as a two-electron electrocyclic ring opening. It is actually a four-electron electrocyclic ring opening. Thanks to Keyi Liang for reporting this error.


Omitted answer (answer key Chap. 5 end-of-chapter question 3ee)

Two one-electron oxidations occur in this reaction. First, the β-keto ester forms a Mn(III) enolate, and the Mn–O bond undergoes homolytic cleavage to give Mn(II) and an O radical. A series of radical cyclizations takes place to generate a tetracyclic compound with a 3° alkyl radical. This compound transfers one electron to Cu(II) to give a carbocation, which undergoes C–H bond fragmentation to give the observed product.

Thanks to Maithili Pokle for reporting this omission.


Cl not Br (answer key Chap. 6 in-chapter question 6.11)

BrMg+ should be ClMg+. Thanks to You-Chen Lin for reporting this error.


Oxidation state of allyl–Pd complexes (answer key Chap. 6 end-of-chapter question 1b)

The Pd atoms in the two allyl–Pd complexes are in the oxidation state (II), not (0). Thanks to You-Chen Lin for reporting this error.


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