Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis
Chemical Reviews, 2013 · paper · Chemistry
A review of visible-light photoredox catalysis using transition metal complexes, mainly ruthenium and iridium, which use light to drive single-electron transfer with organic molecules. It surveys applications in organic synthesis.
6 findings
Substance Section 5.9 names the substrate "N-phenyltetrahydroquino-line (124)", but Scheme 73 draws N-phenyl-1,2,3,4-tetrahydroisoquinoline (labelled 122).
- p. 37 Section 5.9
N-phenyltetrahydroquino-line
- p. 129 Scheme 73
122
- p. 37 Section 5.9
N-phenyltetrahydroquino-line (124)
Judge's note: Page 37 image shows 'N-phenyltetrahydroquino-line'; the hyphen is only a line break, and there is no 'iso'. The Scheme 73 image (p129) shows the N-Ph group in the saturated ring with a CH2 between the arene and N at C1, i.e. a tetrahydroisoquinoline. Quinoline and isoquinoline are different heterocycles, so the text names the wrong compound.
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Substance "catalysts that are more strongly oxidizing than Ir[dF(CF3)ppy](dtbbpy)+ ... such as Ru(bpy)32+ (ET = 46.8 kcal/mol)" conflicts with Table 1, which gives +0.77 V for Ru(bpy)32+ against +1.21 V for the Ir catalyst.
- p. 42 Section 6, first paragraph
catalysts that are more strongly oxidizing than Ir[dF(CF3)ppy](dtbbpy)+, but that possess lower triplet state energies (ET), such as Ru(bpy)3 2+
- p. 141 Table 1, entries 3 and 5, E1/2(M*/M−) column
+0.77
- p. 42 Section 6, paragraph on Scheme 81
catalysts that are more strongly oxidizing than Ir[dF(CF3)ppy](dtbbpy)+, but that possess lower triplet state energies (ET), such as Ru(bpy)32+ (ET = 46.8 kcal/mol)
- p. 42 Section 6, same paragraph
iridium catalyst (E1/2*III/II = +1.21 V vs SCE)
Only the authors can say what is right here.
Judge's note: Table 1 (p141) gives E1/2(M*/M−): Ru(bpy)3 2+ +0.77, Ir[dF(CF3)ppy]2(dtbbpy)+ +1.21, Ru(bpz)3 2+ +1.45. The ground-state E1/2(M+/M) values are Ru(bpy)3 +1.29 and Ir +1.69. On the same page, p42 quotes +1.21 V for the Ir catalyst. By the paper's own data, only Ru(bpz)3 2+ is more strongly oxidizing. The authors should say how the sentence was meant: they could drop Ru(bpy)3 2+ from the example or rephrase it.
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Reference or label Section 5.9 reads "N-phenyltetrahydroquino-line (124) ... the amine radical cation 125 (Scheme 73) ... Deprotonation at the benzylic position of 125", but Scheme 73 labels the substrate N-phenyltetrahydroisoquinoline 122 and its radical cation 123.
- p. 37 Section 5.9, paragraph after eq 11
N-phenyltetrahydroquino-line (124) reductively quenches
- p. 37 Section 5.9
the amine radical cation 125
- p. 129 Scheme 73
122
- p. 37 Section 5.9, first paragraph
N-phenyltetrahydroquino-line (124)
Judge's note: In the p37 crop the text uses 124 and 125. In the Scheme 73 image (p129) the tetrahydroisoquinoline substrate is labelled 122 and its radical cation 123. Section 4.4 also has "N-phenyltetrahydroisoquinoline (122) to its radical cation 123" (text layer, p17). On p18 (crop), 124 is the iminium intermediate and 125 the nitromethane anion. The other numbers in the passage (337–339) match the scheme. The text also says tetrahydroquinoline where the scheme draws a tetrahydroisoquinoline.
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Reference or label Section 5.9 labels the amine and its radical cation "(124)" and "125", but Scheme 73 labels them 122 and 123; in section 4.4, 124 and 125 are the iminium ion and the nitromethane anion.
- p. 37 Section 5.9
(124) reductively quenches the photoexcited species *Ir(ppy)2(dtbbpy)+ to give IrII(ppy)2(dtbbpy) and the amine radical cation 125
- p. 129 Scheme 73
123
- p. 18 Section 4.4
iminium intermediate 124. Addition of the nitromethane anion 125
Judge's note: The p37 image shows 'tetrahydroquino-line (124)', 'amine radical cation 125' and 'Deprotonation at the benzylic position of 125'. The Scheme 73 image (p129) labels these structures 122 and 123. The p18 image shows that 124 is the iminium intermediate and 125 is the nitromethane anion. So the compound numbers in the text point to the wrong structures.
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Reference or label Reference 6 reads "Kalyanasundaram K, Grätzel M. Coord. Chem. Rev. 1998; 77:347.", a volume number lower than the 1988 volume 84 in ref 2.
- p. 46 Reference 6
Kalyanasundaram K, Grätzel M. Coord. Chem. Rev. 1998; 77:347.
- p. 46 Reference 2
Coord. Chem. Rev. 1988; 84:85.
- p. 46 Reference 6
Coord. Chem. Rev. 1998; 77:347
- p. 46 Reference 6
Coord. Chem. Rev. 1998; 77:347.
Only the authors can say what is right here.
Judge's note: Rests on outside knowledge: the real citation is Coord. Chem. Rev. 1998, 177, 347. Within the file, the p46 image shows ref 1 as 1982; 46, ref 2 as 1988; 84, ref 5 as 2010; 254 and ref 6 as 1998; 77. A 1998 volume cannot be numbered below the 1988 one, so either the year or the volume is wrong, and the volume is the likely error.
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Wording The text says "dialkyl phosphates such as 130 to give amino phosphonates", but Scheme 30 draws 130 as (EtO)2P(O)H, a dialkyl phosphite (H-phosphonate).
- p. 18 Section 4.4, second paragraph
dialkyl phosphates such as 130 to give amino phosphonates
- p. 85 Scheme 30, reagent 130
130
Judge's note: The p18 crop has the quoted wording. On the p85 Scheme 30 image, 130 is diethyl phosphite (EtO)2P(O)H, and product 131 has a C–P(O)(OEt)2 bond. The class name in the text does not match the structure drawn.
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18 minor (typos and the like; most checked by the judge only)
Typo Corresponding-author footnote ends with a doubled period: "dmacmill@princeton.edu.."
- p. 1 Footnote, corresponding author
dmacmill@princeton.edu..
Judge's note: In the p1 crop the footnote reads "*Corresponding Author dmacmill@princeton.edu..", with two periods. This is a cosmetic punctuation error.
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Typo MV2+ is called "dimethyl viologen (MV2+)" (p7, twice, and the Scheme 9 title) but "methyl viologen" for MV•+ in the same paragraph and for MV2+ on p34.
- p. 7 Section 3.2, viologen paragraph
known as dimethyl viologen (MV2+)
- p. 7 Section 3.2
the methyl viologen radical cation (MV•+)
- p. 34 Section 5.6
the electron acceptor methyl viologen (MV2+)
Judge's note: Seen on the p7 crop ("known as dimethyl viologen (MV2+)" ... "the methyl viologen radical cation (MV•+)" ... "The facility with which dimethyl viologen") and the p34 crop ("methyl viologen (MV2+)"). The Scheme 9 title is "Redox Chemistry of Dimethyl Viologen (MV2+)". Both names are used in the literature, so this is a naming inconsistency, not an outright error.
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Typo dtbbpy is expanded as "4,4-di-tert-butyl-2,2′-bipyridine" (p11 and the p45 abbreviations list); it should read 4,4′-di-tert-butyl-2,2′-bipyridine.
- p. 11 Section 3.5
dtbbpy = 4,4-di-tert-butyl-2,2′-bipyridine
- p. 45 Abbreviations list
4,4-di-tert-butyl-2,2′-bipyridine
Judge's note: Both crops show a prime on 2,2′ but none on the second 4. In the same list, menbpy is printed "4,4′-dimenthoxycarbonyl-2,2′-bipyridine", so the missing prime is on the page and not an extraction loss.
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Typo Missing article: "As the phenyl C–C bond is most σ-donating bond at the β-position" should read "is the most σ-donating bond".
- p. 12 Section 3.6, Guindon model
As the phenyl C–C bond is most σ-donating bond at the β-position
Judge's note: The p12 crop shows the text as quoted.
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Typo "N-(acyloxyl)-phthalimide 348" does not match "N-(acyloxy)phthalimide", the form used in the same paragraph and in section 3.7.
- p. 39 Section 5.9, aplyviolene paragraph
N-(acyloxyl)-phthalimide 348
- p. 39 Section 5.9, aplyviolene paragraph
reduces N-(acyloxyl)-phthalimide 348
- p. 12 Section 3.7
N-(acyloxy)phthalimides may be used as a masking group
Judge's note: The crop from p39 shows 'N-(acyloxyl)-phthalimide' printed. The text layer has 'N-(acyloxy)phthalimide' on lines 552, 555, 1809 and 1817, including the sentence just before this one. This is a cosmetic spelling inconsistency.
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Typo The excited-state couple is printed "E1/2III/II* = –0.45 V vs SCE" (p16), unlike the "III/*II" notation used elsewhere in the review.
- p. 16 Section 4.3, Ohkubo paragraph
E1/2III/II* = –0.45 V vs SCE
Judge's note: The p16 crop shows the superscript as III/II*. The text layer also has E1/2III/*II for Ru(bpy)3 2+ (p3) and Ru(phen)3 2+, and II/*I is used on p22, so the notation here is inconsistent. This is cosmetic.
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Typo Missing word: "photoredox ATRA reactions have also achieved using the copper photocatalyst" should read "have also been achieved".
- p. 22 End of Section 5.1
photoredox ATRA reactions have also achieved using the copper photocatalyst
Judge's note: The p22 crop shows "have also / achieved" with no "been".
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Typo "the strongly reducing excited-state *Ir(ppy) (E1/2IV/*III = –1.73 V" is missing the subscript 3; the catalyst is fac-Ir(ppy)3, named in the line above.
- p. 23 Last line of page (α-benzylation)
the strongly reducing excited-state *Ir(ppy) (E1/2
- p. 23 Section 5.2, benzylation paragraph, last line
the strongly reducing excited-state *Ir(ppy)
Judge's note: The p23 crop shows "*Ir(ppy)" with no subscript, while "fac-Ir(ppy)3" one line above has its subscript.
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Typo Misspelling: "diaryliodonium salts procceds via a single two-electron oxidation event" should read "proceeds".
- p. 26 Section 5.3.1, last paragraph
diaryliodonium salts procceds via a single two-electron oxidation event
- p. 26
salts procceds via a single two-electron oxidation event
Judge's note: The p26 crop shows "procceds".
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Typo Misspelling: "or electophilic “CF3+” sources" should read "electrophilic".
- p. 28 Section 5.3.3, Ye and Sanford paragraph
or electophilic “CF3+” sources
- p. 28 Section 5.3.3
electophilic “CF3+” sources
- p. 28
or electophilic “CF3+” sources such as S-
Judge's note: The p28 crop shows "electophilic".
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Typo Misspelling: "product 292 in good yield and diasteroselectivity" should read "diastereoselectivity".
- p. 33 Section 5.6
good yield and diasteroselectivity
- p. 33
product 292 in good yield and diasteroselectivity (Scheme 61).151
Judge's note: The p33 crop shows "diasteroselectivity".
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Typo TMEDA is expanded as "Tetramethylenediamine (TMEDA)"; the abbreviation stands for tetramethylethylenediamine.
- p. 36 Section 5.8, second paragraph
Tetramethylenediamine (TMEDA)
Judge's note: The p36 crop shows "Tetramethylenediamine (TMEDA)". The printed name drops "ethyl" and does not match the abbreviation. Because the abbreviation sits alongside it, readers will still identify the reagent, so I rate this as a naming typo.
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Typo Misspelling: "the cylopropyl ring fragments to give the distonic radical cation 334" should read "cyclopropyl".
- p. 36 Section 5.8, Zheng paragraph
the cylopropyl ring fragments
- p. 36
the cylopropyl ring fragments to give the
Judge's note: The p36 crop shows "cylopropyl".
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Typo "Reduction of this species by IrII(ppy)(dtbbpy)" is missing the subscript 2 (Ir(ppy)2(dtbbpy)).
- p. 37 Section 5.9
Reduction of this species by IrII(ppy)(dtbbpy)
- p. 37 Section 5.9
Reduction of this species by IrII(ppy)(dtbbpy) completes
- p. 37 Section 5.9, text on Scheme 73
Reduction of this species by IrII(ppy)(dtbbpy) completes the photocatalytic cycle
- p. 37 Scheme 73 catalytic cycle
IrII(ppy)2(dtbbpy)
Judge's note: The p37 image shows IrII(ppy)(dtbbpy) with no subscript, while earlier in the same paragraph the text has IrII(ppy)2(dtbbpy), and Scheme 73 (p129) shows Ir(ppy)2(dtbbpy). This is a cosmetic slip.
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Typo "(Cp = cyclopentadiene)" should read cyclopentadienyl, since Cp is the ligand in [CpRu(CH3CN)2(CO)]PF6.
- p. 42 Section 6, Osawa paragraph
(Cp = cyclopentadiene)
Judge's note: The p42 image shows '(Cp = cyclopentadiene)'. By standard organometallic nomenclature, the Cp ligand is cyclopentadienyl (C5H5−). This is a minor nomenclature slip.
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Typo "Ir[dF(CF3)ppy](dtbbpy)+" is missing the subscript 2 (Ir[dF(CF3)ppy]2(dtbbpy)+).
- p. 42 Section 6, first paragraph
more strongly oxidizing than Ir[dF(CF3)ppy](dtbbpy)+
- p. 42 Section 6, first paragraph
Ir[dF(CF3)ppy](dtbbpy)+
Judge's note: The p42 image shows the formula with no 2 after the bracket. Lower on the same page the text has Ir[dF(CF3)ppy]2(dtbbpy)+, and Table 1 entry 5 has the 2 as well.
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Typo Reference 15 prints "Stephenson CR. J. Chem. Soc. Rev. 2011; 40:102." and "Stephenson CR. J. Chimia. 2012; 66:394.": the initial J has been split off and attached to the journal name.
- p. 46 Reference 15
Narayanam JMR, Stephenson CR. J. Chem. Soc. Rev. 2011; 40:102.
- p. 46 Reference 15
Stephenson CR. J. Chimia. 2012; 66:394.
Judge's note: The p46 image shows both garbled entries. Elsewhere the same author appears as 'Stephenson CRJ.', for example in refs 13, 23 and 37. The journals are Chem. Soc. Rev. and Chimia.
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Typo References 40, 125a and 114 print "Stephenson CR. J. Chem. Commun.", "Stephenson CR. J. Org. Lett." and "Erra-Balsells RJ. Chem. Soc., Perkin Trans. 2": author initials and journal abbreviations are garbled.
- p. 47 Reference 40
Stephenson CR. J. Chem. Commun. 2013 ASAP
- p. 50 Reference 125a
Stephenson CR. J. Org. Lett. 2010; 12:368.
- p. 49 Reference 114
Erra-Balsells RJ. Chem. Soc., Perkin Trans. 2. 2000:1583.
Judge's note: The crops from p47, p50 and p49 show the printed text. Ref 125b on the same line has the correct form, 'Stephenson CRJ. Org. Lett.'. In ref 114 the 'J.' of 'J. Chem. Soc.' has been merged into the author's initials. These are cosmetic formatting errors in the citations, the same kind of error as C025 but in different references.
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