Copper-Catalyzed Diastereo- and Enantioselective Borylative Cyclization
Round 1
Reviewer 1 Report
Please find the attached file.
Comments for author File: 
Comments.pdf
Author Response
Copper-catalyzed borylative cyclization is an important synthetic tool for the synthesis of various complicated organic molecules. This review focuses on the recent examples and progress of this type of reaction. Various examples were well summarized by dividing the reaction modes, which makes this review easy to read and understand the contents. Deep understanding to the related chemistry is helpful for the development of novel transformations, however, reviewer thinks that this manuscript does not have enough quality to be publishing in Catalysis. The main reason of this decision was unmature construction and English sentences.
The reviewer thinks that addition and consideration to following points would be helpful to improve this manuscript.
Comment 1: Many careless mistakes could be found in the manuscript. For example, spelling miss “furter” and “bestowed” in p. 4, “ST-2” in p. 9, and wrong chemical words “a chiral-phosphine alkyl” (an achiral-phosphine would be appropriate words), wrong compound numbers “zz” and ”zw” (they could not be found in the figures) in p. 15. In addition, “diastereoselective selected examples” in Scheme 9 should be changed to “selected examples of diastereoselective reaction”, and “enantioselective selected examples” in Scheme 9 and “C Enantioselective” in Scheme 3 are also required same kind of change. Thoroughly English editing is required before publication.
Author’s reply: I have corrected all my mistakes as per the reviewer’s point. Kindly see the revised manuscript.
I have provided the corrected compound names and corrected headings in Scheme 3 and Scheme 9.
Comment 2. In the introduction section, some sentence for the importance of borylated compounds should be added. In addition, some overlapping of the contents were found. For example: the two sentences highlighted in red exhibit same meanings and can be combined.
“Herein, I will review the copper-catalyzed borylative cyclization of unsaturated hydrocarbon to generate densely functionalized molecules. This copper-catalyzed method has emerged as a rapidly growing field for the borofunctionalization and intramolecular cyclization of a wide range of hydrocarbons. In this review, the copper-catalyzed functionalization of unsaturated hydrocarbons and intramolecular cyclization will be discussed.“
Author’s reply: I am thankful to the reviewer for this suggestion. I have rewritten the introduction and modified the last part of the introduction. Please see the revised manuscript.
Comment 3. The works by Ito and Sawamura described in section 4.3 is truly early examples of this chemistry and should be introduced in the first part of this review. Dramatic editing of the introduction order is required.
Author’s reply: Thank you for this suggestion, I modified the introduction and included Ito and Sawamura's work in this part.
Comment 4. Ligand L7, which could be found in Scheme 9, should be changed to dppe (not
dppp).
Author’s reply: Thank you, I corrected the ligand’s name.
Comment 5. The “OR” group in lower part of Scheme 4 should be changed to “OMe”.
Author’s reply: Thank you for pointing out the mistake. Now I have provided the corrected structure in Scheme 4.
Comment 6. The absolute configuration of the chiral products in Scheme 6 were wrong
(opposite).
Author’s reply: Thank you, I have corrected all the structures in Scheme 6.
Comment 7. Ligand employed in Scheme 14 is dppp (be careful if structure of L7 is changed).
Author’s reply: I have corrected the numbering of the ligand and provided the corrected number. Please see the revised manuscript
Author Response File: Author Response.pdf
Reviewer 2 Report
The author presents copper-catalyzed enantioselective borylative cyclization and regiodivergent functionalization of alkenes, allenes, and alkynes in the proposed review.
The review is well organized and structured. However, there are some more literature data available and highly appreciated in this field that should be mentioned. Furthermore, more detailed mechanistic insight would be highly appreciated since the review would have more impact on a wider audience. I suggest the insertion of schemes that support the mechanism.
Due to the above mentioned I suggest major revision.
Author Response
Comments and Suggestions for Authors
The author presents copper-catalyzed enantioselective borylative cyclization and regiodivergent functionalization of alkenes, allenes, and alkynes in the proposed review. The review is well organized and structured. However, there are some more literature data available and highly appreciated in this field that should be mentioned. Furthermore, more detailed mechanistic insight would be highly appreciated since the review would have more impact on a wider audience. I suggest the insertion of schemes that support the mechanism.
Due to the above mentioned I suggest major revision.
Author’s reply: Thank you for your suggestion. There have been many reports on copper-catalyzed cyclization methods in the past decades. I chose some selective and interesting diastereo- and enantioselective borylative cyclization reactions for this brief review.
Now, I have added mechanisms in Scheme 1, 3A, 5A and 15. I have also provided one interesting reaction from Ito’s group in Scheme 15. Please see the revised Manuscript.
Author Response File: Author Response.pdf
Reviewer 3 Report
The author summarizes the copper-catalyzed intramolecular borylative coupling reactions for the last decades. The presented methods are appropriately grouped, which helps the reader to get familiar with the field.
According to the reviewer, it would be helpful to visualize the chemical structure of B2pin2 and Bpin in Figure 1 and unlock the abbreviations in figure capture.
The author mentions specific examples in Scheme 4B with well-defined yield and ee values, but which R groups are these values belong to? Please define the R groups.
In line 146, the author said, “Excellent regio-, diastereo- and enantioselectivity values were achieved. Based on Scheme 6 ee earn higher values than 90% in only two cases. Please rephrase this sentence “Moderate to excellent …” or cite examples with ee>90%.
The title of chapters 3.1 and 3.3 are the same, and also 3.2 and 3.4. Please distinguish chapter titles. For example, based on the ring system is formed is condensed or detached.
According to the reviewer’s observation, Scheme 11 is not referenced in the main text. Please replace it in the appropriate section.
In line 274, there is a typo, a double e in cyclopropane.
Typos and minor errors:
Please write “styrenes” instead of “syrenes” in line 50.
In many cases, the hyphen is missing from 2,3-disubstituted-… molecule names (e.g., lines 50, 54, 70,73). Please check up the whole manuscript.
Please change the point to coma in line 75 at “1.3-dienes)
Please add NHC to the abbreviations.
Author Response
The author summarizes the copper-catalyzed intramolecular borylative coupling reactions for the last decades. The presented methods are appropriately grouped, which helps the reader to get familiar with the field.
Comment 1. According to the reviewer, it would be helpful to visualize the chemical structure of B2pin2 and Bpin in Figure 1 and unlock the abbreviations in figure capture.
Author’s reply: I am thankful to the reviewer for this suggestion. I have provided the chemical structure of B2pin2 and Bpin in Figure
Comment 2. The author mentions specific examples in Scheme 4B with well-defined yield and ee values, but which R groups are these values belong to? Please define the R groups.
Author’s reply: Now, I have provided the corrected structure of the R group in Scheme 4B
Comment 3. In line 146, the author said, “Excellent regio-, diastereo- and enantioselectivity values were achieved. Based on Scheme 6 ee earn higher values than 90% in only two cases. Please rephrase this sentence “Moderate to excellent …” or cite examples with ee>90%.
Author’s reply: I have modified the sentence. Thank you for the suggestion.
Comment 4. The title of chapters 3.1 and 3.3 are the same, and also 3.2 and 3.4. Please distinguish chapter titles. For example, based on the ring system is formed is condensed or detached.
Author’s reply: I have modified the chapter titles.
Comment 5. According to the reviewer’s observation, Scheme 11 is not referenced in the main text. Please replace it in the appropriate section.
Author’s reply: Now, I have referenced the Scheme 11 in the main text.
Comment 6. In line 274, there is a typo, a double e in cyclopropane.
Author’s reply: I have corrected the typo mistake.
Comment 7. Please write “styrenes” instead of “syrenes” in line 50.
Author’s reply: I have corrected the typo mistake.
Comment 8. In many cases, the hyphen is missing from 2,3-disubstituted-… molecule names (e.g., lines 50, 54, 70,73). Please check up the whole manuscript.
Author’s reply: I have corrected typo mistakes and checked the whole manuscript.
Comment 9. Please change the point to coma in line 75 at “1.3-dienes)
Author’s reply: I have corrected it.
Comment 10. Please add NHC to the abbreviations.
Author’s reply: I have added NHC to the abbreviations.
Author Response File: Author Response.pdf
Round 2
Reviewer 1 Report
The authors well respond my suggestion and now this manuscript has enough quality to be publishing in Catalysis after addressing some points the listed below.
1. compound number A and B were observed many times in the mechanistic discussion. Please correct.
2. Even in the revised version, some spelling miss could be found such as “vai” in line 345 in p. 18 and “reduction” in line 351 in p.19. Thoroughly English checking is required before publication.
Author Response
The authors well respond my suggestion and now this manuscript has enough quality to be publishing in Catalysis after addressing some points the listed below.
Author’s reply: I am extremely delighted to hear the feedback. I was able to increase the manuscript's quality thanks to the reviewer's thoughtful remarks.
Comment 1, compound number A and B were observed many times in the mechanistic discussion. Please correct.
Author’s reply: I am thankful to the reviewer for this suggestion. I have rectified this mistake.
Comment 2, Even in the revised version, some spelling miss could be found such as “vai” in line 345 in p. 18 and “reduction” in line 351 in p.19. Thoroughly English checking is required before publication.
Author’s reply: Thank you for the suggestion, I have corrected these mistakes.
I acknowledge the reviewer for this suggestion. I have gone through all the text and checked for English mistakes.
Author Response File: 
Author Response.docx
Reviewer 2 Report
I accept the manuscript in its current form.
Author Response
Comments and Suggestions for Authors
I accept the manuscript in its current form.
Author’s reply: I am extremely delighted to hear the feedback. Thank you for your suggestion to accept this interesting review in Catalysis.
Author Response File: Author Response.docx
