Copper-Catalyzed/Hypervalent Iodine-Mediated Functionalization of Unactivated Compounds
Round 1
Reviewer 1 Report
Loro and Broggini et al., present a comprehensive review on copper-catalyzed hypervalent iodine-mediated functionalization reactions. While I believe this article holds potential utility for research in this field, the quality of the schematic representations necessitates substantial improvements. Therefore, I recommend revisiting the manuscript after undertaking major revisions. Below are my detailed suggestions:
1. Introduction: There are already multiple review articles published on the subject of hypervalent iodine chemistry (e.g. Chem. Rev. 2016, 116, 5, 3328–3435; Adv. Synth. Catal. 2022, 364, 1798). I advise the authors to address these prior reviews and elucidate the unique contributions of their work.
2. Scheme: If the reaction depicted in a scheme is enantioselective or diastereoselective, please provide the range of ee/dr values. Moreover, ensure to specify whether the structure given in the scheme denotes relative or absolute stereochemistry, using appropriate indications (wedge and dash for absolute; solid and broken bar for relative).
3. Citations: Adhere to the citation formatting of the Catalyst journal, which uses ordinary numbers instead of Roman numerals.
Additionally, the schemes contain numerous errors. I urge the authors to thoroughly reexamine all the schemes. Here are some of the errors I spotted. However, given the time constraints, there may be additional mistakes that I have overlooked:
4. Scheme 4: The positions of R1 and R2 need to be interchanged for the substrates on the left panel.
5. Scheme 7: The structure of the bis(oxazoline) ligand is absent. Reaction yields are also missing.
6. Scheme 8: The substrate scope for the Ar group has been overlooked.
7. Scheme 19: Based on the cited reference, the reaction conditions for the first row substrates and the reaction mechanism diverge from the ones listed in the scheme. In the bottom mechanism, Cu(II) should be Cu(III), and the ligand (L) is not specified for the bottom Cu(III) species.
8. Scheme 26: The positions of Ar1 and R2 should be swapped in the second reaction.
9. Scheme 27: The R group is not defined.
10. Scheme 39: In step 1, replace -NH2 with -Br for the substrate above the arrow. In compound 38, the R1 group is absent from the terminal position.
11. Scheme 47: The R2 group is missing in several intermediates in the reaction mechanism.
12. Scheme 71: The structure of compound 58 is incorrect; there should only be one C=C bond instead of two.
13. Scheme 107: The mechanism needs revision. Reductive elimination of LVII cannot yield the final product.
14. Scheme 108: The amide group is missing in the structure of LVIII.
15. Scheme 111: The reaction should read Ar2Cu(III)X -> ArCu(III) + X.
16. Scheme 114: Recheck the structure of LXV. The final product cannot be obtained based on this mechanism.
17. Schemes 125 & 130: Substrate scopes have not been provided.
Minor errors:
1. Line 255: Omit the word "always".
2. Line 759: Change "di" to "in".
Author Response
Dear Ms. Zhao,
Thank you very much for your response about our manuscript ID: catalysts-2555811 entitled “Copper-Catalyzed/Hypervalent Iodine-Mediated Functionalization of Unactivated Compounds” and for your availability in considering a new version of it. We are also thankful for the reviewers’ efforts made to improve the manuscript.
Accordingly, we are now submitting a new version of the manuscript, revised according to the reviewers’ comments/suggestions. Changes in the new version of the manuscript are highlighted in yellow.
Here below a point-by-point list of the reviewers questions/remarks, followed by our answers.
Reviewer 1:
Comment 1. Introduction: There are already multiple review articles published on the subject of hypervalent iodine chemistry (e.g. Chem. Rev. 2016, 116, 5, 3328–3435; Adv. Synth. Catal. 2022, 364, 1798). I advise the authors to address these prior reviews and elucidate the unique contributions of their work.
Answer Additional reviews [8-12] regarding the chemistry of hypervalent iodine have been added.
Comment 2. Scheme: If the reaction depicted in a scheme is enantioselective or diastereoselective, please provide the range of ee/dr values. Moreover, ensure to specify whether the structure given in the scheme denotes relative or absolute stereochemistry, using appropriate indications (wedge and dash for absolute; solid and broken bar for relative).
Answer The range of ee or dr was added in schemes where the following were missing.
Comment 3. Citations: Adhere to the citation formatting of the Catalyst journal, which uses ordinary numbers instead of Roman numerals.
Answer The format of citations has been checked.
Comment Additionally, the schemes contain numerous errors. I urge the authors to thoroughly reexamine all the schemes. Here are some of the errors I spotted. However, given the time constraints, there may be additional mistakes that I have overlooked:
- Scheme 4: The positions of R1and R2need to be interchanged for the substrates on the left panel.
- Scheme 7: The structure of the bis(oxazoline) ligand is absent. Reaction yields are also missing.
- Scheme 8: The substrate scope for the Ar group has been overlooked.
- Scheme 19: Based on the cited reference, the reaction conditions for the first row substrates and the reaction mechanism diverge from the ones listed in the scheme. In the bottom mechanism, Cu(II) should be Cu(III), and the ligand (L) is not specified for the bottom Cu(III) species.
- Scheme 26: The positions of Ar1and R2should be swapped in the second reaction.
- Scheme 27: The R group is not defined.
- Scheme 39: In step 1, replace -NH2with -Br for the substrate above the arrow. In compound 38, the R1group is absent from the terminal position.
- Scheme 47: The R2group is missing in several intermediates in the reaction mechanism.
- Scheme 71: The structure of compound 58 is incorrect; there should only be one C=C bond instead of two.
- Scheme 107: The mechanism needs revision. Reductive elimination of LVII cannot yield the final product.
- Scheme 108: The amide group is missing in the structure of LVIII.
- Scheme 111: The reaction should read Ar2Cu(III)X -> ArCu(III) + X.
- Scheme 114: Recheck the structure of LXV. The final product cannot be obtained based on this mechanism.
- Schemes 125 & 130: Substrate scopes have not been provided.
Minor errors:
- Line 255: Omit the word "always".
- Line 759: Change "di" to "in". Line 721
Answer Schemes were rechecked and all notes by the reviewer were accepted and corrected.
The new version of the manuscript should now fulfill the requirements for publication in Catalysts. Looking forward to hearing from you at your earliest convenience.
Sincerely yours,
Prof. Gianluigi Broggini
Reviewer 2 Report
To
The Catalysts Editorial Office
Here I am sending the review report on catalysts-2420074.
The functionalization of unactuated substrates through the combination of copper catalysts and hypervalent iodine reagents represents a versatile tool in organic synthesis to access various classes of compounds. The review by Gianluigi Broggini his colleagues report the study entitled “Copper-Catalyzed/Hypervalent Iodine-Mediated Functionalization of Unactivated Compounds.” I hope this review will provide more information on functionalization of unactivated substrates through the combination of copper catalysts and hypervalent iodine reagents. I have carefully evaluated the review. I found that this review article is suitable to publish in the catalysts after minor revision.
I have gone through the J. Am. Chem. Soc. 2008, 130, 8172-8174. DOI: 10.1021/ja801767s, according to the paper authors should correct structure III in scheme 6.
Authors should show the atropoisomer of structure 3 in scheme 7. It confuses the readers.
Authors should check the structure IX in scheme 11.
Correct the drawings of scheme 13 and 14.
Authors should correct structure 58 in scheme 71.
Authors should check and correct the mechanism in scheme 77.
Authors should check intermediate LVII in scheme 107.
Scheme 112, structure 26 number is wrong author should check.
Authors have not covered the few papers on “Copper-Catalyzed/Hypervalent Iodine benziodoxol(on)es or iodonium salts Mediated Functionalizations.” Here I have mentioned a few of them. Authors should check the literature.
Enantioselective Synthesis of Axially Chiral Biaryls via Cu-Catalyzed Acyloxylation of Cyclic Diaryliodonium Salts (ACS Catal. 2019, 9, 6, 4951–4957)
Copper-Catalyzed Selective Diphenylation of Carboxylic Acids with Cyclic Diaryliodonium Salts (J. Org. Chem. 2017, 82, 10, 5250–5262)
Synthesis of Functionalized Biaryls and Poly(hetero)aryl Containing Medium-Sized Lactones with Cyclic Diaryliodonium Salts (Org. Lett. 2017, 19, 10, 2600–2603)
Construction of Functionalized Annulated Sulfone via SO2/I Exchange of Cyclic Diaryliodonium Salts (Org. Lett. 2017, 19, 18, 4916–4919)
Enantioselective α-Arylation of Cyclohexanones with Diaryl Iodonium Salts: Application to the Synthesis of (−)-Epibatidine (Angew. Chem., Int. Ed., 2005, 44, 5516–5519)
Copper-Catalyzed Diphenylation of P(O)-OH Bonds with Cyclic Diaryliodonium Salts (https://doi.org/10.1002/asia.201901284)
Enantioselective Ring-Opening/Oxidative Phosphorylation and P‑Transfer Reaction of Cyclic Diaryliodoniums (ACS Catal. 2019, 9, 9852−9858)
Copper-Catalyzed Asymmetric Ring-Opening of Cyclic Diaryliodonium with Benzylic and Aliphatic Amines (https://doi.org/10.1002/adsc.201800637)
Copper-Catalyzed Enantioselective Ring-Opening of Cyclic Diaryliodoniums and O-Alkylhydroxylamines (Org. Lett. 2019, 21, 16, 6374–6377)
Mild Cu(I)-Catalyzed Cascade Reaction of Cyclic Diaryliodoniums,Sodium Azide, and Alkynes: Efficient Synthesis ofTriazolophenanthridines (10.1021/ol502654a|Org.Lett.2014, 16, 5600)
Atroposelective Ring Opening of Cyclic Diaryliodonium Salts with Bulky Anilines Controlled by a Chiral Cobalt(III) Anion (https://doi.org/10.1002/anie.202008431)
Catalytic Asymmetric Synthesis of Atropisomeric Nitrones: Versatile Intermediate for Axially Chiral Biaryls (Org. Lett. 2020, 22, 19, 7622–7628)
Cu-Catalyzed Site-Selective and Enantioselective Ring Opening of Cyclic Diaryliodoniums with 1,2,3-Triazoles (Org. Lett. 2020, 22, 16, 6441–6446)
Enantioselective preparation of atropisomeric biaryl trifluoromethylsulfanes via ring-opening of cyclic diaryliodoniums (Chem. Commun., 2021, 57, 3881–38840)
Discovery of Stabilized Bisiodonium Salts as Intermediates in the Carbon–Carbon Bond Formation of Alkyne (Angew. Chem., Int. Ed., 2011, 50, 3784–3787)
Hexafluoroisopropanol-Enabled Copper-Catalyzed Asymmetric Halogenation of Cyclic Diaryliodoniums for the Synthesis of Axially Chiral 2,2′-Dihalobiaryls (Org. Lett. 2021, 23, 2, 329–333)
Regiocontrolled Direct C−H Arylation of Indoles at the C4 and C5 Positions (https://doi.org/10.1002/anie.201612599)
Cu-catalyzed Cascade Cyclization of Isothiocyanates, Alkynes, and Diaryliodonium Salts: Access to Diversely Functionalized Quinolines (https://doi.org/10.1002/chem.201702364)
Design, development and applications of coppercatalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkyne (https://doi.org/10.1038/s42004-022-00768-3)
A copper-catalyzed arylation of tryptamines for the direct synthesis of aryl pyrroloindolines
(https://doi.org/10.1039/C2SC20914D)
Copper-Catalyzed C-2 Arylation or Vinylation of Indole Derivatives with Iodonium Salts (https://doi.org/10.1002/asia.201402071)
Selective Synthesis of ortho-Substituted Diarylsulfones by Using NHC-Au Catalysts under Mild Conditions (Org. Lett. 2019, 21, 4, 974–979)
Comments for author File: 
Comments.pdf
The quality of the English is acceptable, but typos should be corrected
Author Response
Reviewer 2:
Comment I have gone through the J. Am. Chem. Soc. 2008, 130, 8172-8174. DOI: 10.1021/ja801767s, according to the paper authors should correct structure III in scheme 6.
Answer Structure III of Scheme 6 has been corrected.
Comment Authors should show the atropoisomer of structure 3 in scheme 7. It confuses the readers.
Answer Structure 3 in Scheme 7 has been fixed.
Comment Authors should check the structure IX in scheme 11.
Answer Structure IX in Scheme 11 has been corrected.
Comment Correct the drawings of scheme 13 and 14.
Answer Schemes 13 and 14 have been corrected.
Comment Authors should correct structure 58 in scheme 71.
Answer Structure 58 has been corrected.
Comment Authors should check and correct the mechanism in scheme 77.
Answer Mechanism in Scheme 77 has been corrected.
Comment Authors should check intermediate LVII in scheme 107.
Answer Intermediate LVII in Scheme 110 has been corrected.
Comment Scheme 112, structure 26 number is wrong author should check.
Answer Structure 26 in Scheme 112 (now Scheme 115) has been changed into 84.
Comment Authors have not covered the few papers on “Copper-Catalyzed/Hypervalent Iodine benziodoxol(on)es or iodonium salts Mediated Functionalizations.” Here I have mentioned a few of them. Authors should check the literature.
Comment Enantioselective Synthesis of Axially Chiral Biaryls via Cu-Catalyzed Acyloxylation of Cyclic Diaryliodonium Salts (ACS Catal. 2019, 9, 6, 4951–4957)
Answer This paper has been inserted as Reference 145.
Comment Copper-Catalyzed Selective Diphenylation of Carboxylic Acids with Cyclic Diaryliodonium Salts (J. Org. Chem. 2017, 82, 10, 5250–5262)
Answer This paper has been inserted as Reference 144.
Comment Synthesis of Functionalized Biaryls and Poly(hetero)aryl Containing Medium-Sized Lactones with Cyclic Diaryliodonium Salts (Org. Lett. 2017, 19, 10, 2600–2603)
Answer This paper was not included because it does not involve copper catalysis.
Comment Construction of Functionalized Annulated Sulfone via SO2/I Exchange of Cyclic Diaryliodonium Salts (Org. Lett. 2017, 19, 18, 4916–4919)
Answer This paper has been inserted as Reference 164.
Comment Enantioselective α-Arylation of Cyclohexanones with Diaryl Iodonium Salts: Application to the Synthesis of (−)-Epibatidine (Angew. Chem., Int. Ed., 2005, 44, 5516–5519)
Answer This paper was not included because it does not involve copper catalysis.
Comment Copper-Catalyzed Diphenylation of P(O)-OH Bonds with Cyclic Diaryliodonium Salts (https://doi.org/10.1002/asia.201901284)
Answer This paper has been inserted as Reference 147.
Comment Enantioselective Ring-Opening/Oxidative Phosphorylation and P‑Transfer Reaction of Cyclic Diaryliodoniums (ACS Catal. 2019, 9, 9852−9858)
Answer This paper has been inserted as Reference 148.
Comment Copper-Catalyzed Asymmetric Ring-Opening of Cyclic Diaryliodonium with Benzylic and Aliphatic Amines (https://doi.org/10.1002/adsc.201800637)
Answer This paper has been inserted as Reference 125.
Comment Copper-Catalyzed Enantioselective Ring-Opening of Cyclic Diaryliodoniums and O-Alkylhydroxylamines (Org. Lett. 2019, 21, 16, 6374–6377)
Answer This paper has been inserted as Reference 127.
Comment Mild Cu(I)-Catalyzed Cascade Reaction of Cyclic Diaryliodoniums,Sodium Azide, and Alkynes: Efficient Synthesis ofTriazolophenanthridines (10.1021/ol502654a|Org.Lett.2014, 16, 5600)
Answer This paper has been inserted as Reference 169.
Comment Atroposelective Ring Opening of Cyclic Diaryliodonium Salts with Bulky Anilines Controlled by a Chiral Cobalt(III) Anion (https://doi.org/10.1002/anie.202008431)
Answer This paper has been inserted as Reference 126.
Comment Catalytic Asymmetric Synthesis of Atropisomeric Nitrones: Versatile Intermediate for Axially Chiral Biaryls (Org. Lett. 2020, 22, 19, 7622–7628)
Answer This paper has been inserted as Reference 129.
Comment Cu-Catalyzed Site-Selective and Enantioselective Ring Opening of Cyclic Diaryliodoniums with 1,2,3-Triazoles (Org. Lett. 2020, 22, 16, 6441–6446)
Answer This paper has been inserted as Reference 128.
Comment Enantioselective preparation of atropisomeric biaryl trifluoromethylsulfanes via ring-opening of cyclic diaryliodoniums (Chem. Commun., 2021, 57, 3881–38840)
Answer This paper has been inserted as Reference 166.
Comment Discovery of Stabilized Bisiodonium Salts as Intermediates in the Carbon–Carbon Bond Formation of Alkyne (Angew. Chem., Int. Ed., 2011, 50, 3784–3787)
Answer This paper was not included because it does not involve copper catalysis.
Comment Hexafluoroisopropanol-Enabled Copper-Catalyzed Asymmetric Halogenation of Cyclic Diaryliodoniums for the Synthesis of Axially Chiral 2,2′-Dihalobiaryls (Org. Lett. 2021, 23, 2, 329–333)
Answer This paper has been inserted as Reference 176.
Comment Regiocontrolled Direct C−H Arylation of Indoles at the C4 and C5 Positions (https://doi.org/10.1002/anie.201612599)
Answer This paper has been inserted as Reference 35.
Comment Cu-catalyzed Cascade Cyclization of Isothiocyanates, Alkynes, and Diaryliodonium Salts: Access to Diversely Functionalized Quinolines (https://doi.org/10.1002/chem.201702364)
Answer This paper has been inserted as Reference 167.
Comment Design, development and applications of coppercatalyzed regioselective (4 + 2) annulations between diaryliodonium salts and alkyne (https://doi.org/10.1038/s42004-022-00768-3)
Answer This paper has been inserted as Reference 168.
Comment A copper-catalyzed arylation of tryptamines for the direct synthesis of aryl pyrroloindolines (https://doi.org/10.1039/C2SC20914D)
Answer This paper has been inserted as Reference 168.
Comment Selective Synthesis of ortho-Substituted Diarylsulfones by Using NHC-Au Catalysts under Mild Conditions (Org. Lett. 2019, 21, 4, 974–979)
Answer This paper was not included because it does not involve copper catalysis.
The new version of the manuscript should now fulfill the requirements for publication in Catalysts. Looking forward to hearing from you at your earliest convenience.
Sincerely yours,
Prof. Gianluigi Broggini
Round 2
Reviewer 1 Report
All my concerns have been addressed; I would like to accept it as present form.
