Nickel-Catalyzed Cross-Coupling of Photoredox-Generated Radicals: Uncovering a General Manifold for Stereoconvergence in Nickel-Catalyzed Cross-Couplings
2015 · paper · Chemistry
Uses density functional theory to study the mechanism of photoredox/nickel dual-catalyzed cross-coupling of alkyltrifluoroborates. Calculations suggest an additional alkylnickel(I) pathway and a stereoselectivity route via dynamic kinetic resolution of a Ni(III) intermediate, possibly general to other nickel couplings.
2 findings
Reference or label Reference 8b: "Angew. Chem., Int. Ed. 2014, 54, 1082" pairs year 2014 with volume 54, while reference 18b gives "Angew. Chem., Int. Ed. 2009, 48, 2656"; at one volume per year, volume 54 is 2015.
- p. 4 References, ref 8b
Angew. Chem., Int. Ed. 2014, 54, 1082
- p. 4 References, ref 18b
Angew. Chem., Int. Ed. 2009, 48, 2656
- p. 4 References, ref 8b
2014, 54, 1082
Only the authors can say what is right here.
Judge's note: Rests on outside knowledge: that Angew. Chem. Int. Ed. publishes exactly one volume per calendar year, and which of year or volume is the wrong one for the cited article. Both entries read as quoted on the page 4 image. The paper's own ref 18b (2009, vol 48) implies vol 54 = 2015 and 2014 = vol 53, so the year and volume in 8b cannot both be right; an online-first 2014 date would explain it. The authors need to say which element to correct.
Second check: another model agreed
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Reference or label Reference 8b has a garbled author list: "Leonori, D.; Varinder K; Aggarwal, V. K. Angew. Chem., Int. Ed. 2014, 54, 1082." The entry 'Varinder K' looks like a stray duplicate of Aggarwal's given names.
- p. 4 References, ref 8b
Leonori, D.; Varinder K; Aggarwal, V. K.
- p. 4 References, ref 8b
Leonori, D.; Varinder K; Aggarwal, V. K. Angew. Chem., Int. Ed. 2014, 54, 1082.
- p. 4
(b) Leonori, D.; Varinder K; Aggarwal, V. K. Angew.
Only the authors can say what is right here.
Judge's note: Rests on outside knowledge: that Aggarwal's given name is Varinder and that Angew. Chem. Int. Ed. volume 54 is 2015. On the page 4 image, 'Varinder K' is printed between Leonori and Aggarwal. It does not follow the surname-plus-initials format used for every other author in the reference list, and it matches the initials V. K. of the next author. The year 2014 printed with volume 54 may conflict with the volume, but this cannot be checked from the files and could be the online-first date. The authors should confirm the author list and the year.
Second check: another model agreed
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7 minor (typos and the like; most checked by the judge only)
Wording Page 2: "intermediate B1, which proceeds via a ∼5 kcal/mol energy barrier to form benzylnickel-(I) intermediate B2"; Figure 2 gives B1 3.3 (-1.8) and B1-TS 4.8 (4.6), so the barrier from B1 is 1.5 (6.4) kcal/mol, and ∼5 matches only B1-TS measured from A.
- p. 2 Right column, alternative pathway paragraph
proceeds via a ∼5 kcal/mol energy barrier to form benzylnickel-
- p. 2 Figure 2, B1 and B1-TS
3.3
- p. 2 Figure 2, B1 and B1-TS labels
B1-TS 4.8 (4.6); B1 3.3 (-1.8)
Judge's note: Read Figure 2 on the page 2 image: B1 3.3 (-1.8), B1-TS 4.8 (4.6), B2 -10.2 (-15.9), A2 -25.6 (-26.5), A2-TS -22.7 (-22.5), A1-TS 18.2 (14.7). The ∼5 figure equals the height of B1-TS above the zero reference A (4.8/4.6). The same sentence's "favorable by ∼10-15 kcal/mol" also matches B2 measured from A (-10.2/-15.9), and the oxidative addition "15-18" matches A1-TS from A, so the authors evidently quote this pathway relative to A. The A2-TS "∼4" barrier, by contrast, is measured from the preceding intermediate A2 (2.9/4.0). The number is therefore defensible but the sentence reads as a barrier from B1, and the reference point is used inconsistently. Wording ambiguity, not a wrong value.
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Wording Page 3: "computations of the diastereomeric transition states C′ corresponding to eq 2" uses the label C′, defined a few lines earlier as "Ni(III) complex C′"; note 16 on the same sentence calls the transition state "C-TS′".
- p. 3 Left column, sentence beginning "Indeed, computations of"
states C′ corresponding to eq 2 correlate well with experiment
- p. 3 Left column, a few lines above
of Ni(III) complex C′.
- p. 4 References, note 16
lowest energy C-TS′
- p. 3 Left column, DKR paragraph
kinetic resolution (DKR)13 of Ni(III) complex C′
Judge's note: Checked the page 3 left column and note 16 on page 4, plus the C / C-TS convention in Figure 2. The label C′ is used for both the intermediate and its reductive-elimination transition states, whereas the paper's own convention is C-TS′. It can be read loosely as 'transition states of C′', and no reader would be misled about the result, so this is a minor labelling inconsistency.
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Typo Page 2, right column: "undertaken to ensure transitions states connected the illustrated ground states" should read "transition states".
- p. 2 Right column, first lines (computational methods paragraph)
transitions states connected the illustrated ground states
- p. 2 Methods paragraph
to ensure transitions states connected the illustrated ground states
Judge's note: Read on the page 2 image, top of right column: "transitions states" is printed. The paper uses "transition states" everywhere else. Plain typo.
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Typo Stray comma in the locant: "dissociation of 1,5,-cyclooctadiene (COD)" should read "1,5-cyclooctadiene".
- p. 2 Right column, paragraph beginning "Beginning from square planar Ni(bpy)(COD) A"
1,5,-cyclooctadiene
- p. 2
dissociation of 1,5,-cyclooctadiene (COD)
- p. 2 Right column, paragraph beginning 'Beginning from square planar'
of 1,5,-cyclooctadiene (COD)
- p. 2 Results paragraph, 'Beginning from square planar...'
1,5,-cyclooctadiene (COD)
Judge's note: I checked the page 2 crop, right column, in the paragraph beginning 'Beginning from square planar Ni(bpy)(COD) A'. The comma after the 5 is printed on the page, so it is not a text-layer artefact. This is a plain typographical slip with an obvious fix.
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Typo Figure 5 caption: "SMD-water-(U)M06/6-311+G(d,p)//B3LYP/6-31G(d) in SMD (water) level of theory" gives the geometry method as B3LYP where the methods text and the captions of Figures 2 and 3 say UB3LYP, and names the SMD water solvation twice.
- p. 3 Figure 5 caption
SMD-water-(U)M06/6-311+G(d,p)//B3LYP/6-31G(d) in SMD (water) level of theory
- p. 3 Figure 3 caption
SMD-water-(U)M06/6-311+G(d,p)//UB3LYP/6-31G(d)
- p. 2 Left column, computational methods
spin-unrestricted broken-symmetry UB3LYP
- p. 2 Methods paragraph
(U)M06/6-311+G(d,p)
Judge's note: Read the Figure 3 and Figure 5 captions on the page 3 image and the methods on page 2 ("all optimizations were performed using a spin-unrestricted broken-symmetry UB3LYP functional"). Figure 5's caption does drop the U and repeats the solvent model. B3LYP is very likely shorthand for the same unrestricted method, so this is a caption inconsistency and a redundant phrase, not a methods discrepancy. The M06 versus M06-2X point raised in one note is covered by C003.
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Typo Page 3: "the "black box" nature of these transformations have limited their widespread development"; singular subject "nature" needs "has limited".
- p. 3 Right column, paragraph beginning "Moving forward"
nature of these transformations have limited their widespread
Judge's note: Read on the page 3 image, right column, paragraph beginning "Moving forward". Subject-verb disagreement; meaning unaffected.
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Typo Reference 5: "Zuo, Z.; Ahneman, D. T.; Chu, L.; Terret, J. A.; Doyle, A. G.; MacMillan, D. W. C. Science 2014, 345, 437" spells the fourth author "Terret"; the surname is believed to be "Terrett".
- p. 4 References, ref 5
Terret, J. A.
Only the authors can say what is right here.
Judge's note: Rests on outside knowledge: that the fourth author of Science 2014, 345, 437 is J. A. Terrett (double t). The page 4 image prints "Terret, J. A." as quoted. The spelling of the cited author cannot be checked from the files, so this goes to the authors.
Second check: none (judge only)