Review Reports

Round 1

Reviewer 1 Report

Comments and Suggestions for Authors

This review describes the different reported methods and approaches to access macro-endoperoxides. This class of compounds is of interest showing sometimes high cytotoxicity on cancer cell lines. The structuration of the review is well organized, ranking the examples by type of method. The reviews indicates clearly the ring size on the macrolactone which is nice for the readers.

A more detail correction is provided as a scanned document

 

The review merits publication after some modifications.

-Authors must take care about past tense. They must stick using past for reporting results, but present tense must use only in the case of facts that are intemporal, e.g., reaction mechanism, or biological activity.

-Example described in Scheme 16 should be displaced to section 4.2 with “peroxidation of carbonyl group.“ Indeed ozonlyisis forms Criegee intermediate which is similar to carbonyl function.

-Some discussions of results are a bit missing sometimes (see scan copies)

-be careful to not confuse ketal (ketone origin) and acetal (aldehyde origin) roots.

-Titles in Scheme 3 (and in the different sections seems for me a bit confusing)

                The term iodocyclization for 2.1 should be added

                The term alkylation for  2.2 should added

                The term Recyclization should be revised. It is very unclear and confusing for me. Probably the terms of “oxycarbenium rearrangement” or “oxycarbenium metathesis” seems more appropriated?

-Be careful to not flip molecules from starting material to final product, that makes the reading more difficult.

-Take care about too light color for Sulfur or Phosphorous atoms

-In introduction, about bibliography, a recent review seems missing:

 

DOI: 10.1016/bs.aihch.2021.03.001

Comments for author File: Comments.pdf

Comments on the Quality of English Language

The document needs some reformulation sometimes. Authors must take attention to the tense used

Author Response

Reviewer 1

This review describes the different reported methods and approaches to access macro-endoperoxides. This class of compounds is of interest showing sometimes high cytotoxicity on cancer cell lines. The structuration of the review is well organized, ranking the examples by type of method. The reviews indicates clearly the ring size on the macrolactone which is nice for the readers.

A more detail correction is provided as a scanned document.

Response: We greatly appreciate your kind words regarding our review. The corrections provided in the scanned document were also taken into account and revised.

 

The review merits publication after some modifications.

-Authors must take care about past tense. They must stick using past for reporting results, but present tense must use only in the case of facts that are intemporal, e.g., reaction mechanism, or biological activity.

Response: The manuscript was revised and rewritten.

 

-Example described in Scheme 16 should be displaced to section 4.2 with “peroxidation of carbonyl group.“ Indeed ozonlyisis forms Criegee intermediate which is similar to carbonyl function.

Response: According to the reviewer’s suggestion, Scheme 16 was moved to section 4.2 (now it is Scheme 44).

 

-Some discussions of results are a bit missing sometimes (see scan copies)

Response: The corrections provided in the scanned document were taken into account and revised.

 

-be careful to not confuse ketal (ketone origin) and acetal (aldehyde origin) roots.

Response: Discussion of Schemes 6, 8, 12 was revised.

 

-Titles in Scheme 3 (and in the different sections seems for me a bit confusing)

Response: Scheme 3 was revised.

 

The term iodocyclization for 2.1 should be added

Response: Section 2.1 was renamed as “Intramolecular iodocyclization of hydroperoxides”.

 

The term alkylation for  2.2 should added

Response: Section 2.2 contains examples not only of alkylation of dihydroperoxides with dihalogenides, but also of condensation of carbonyl compounds, hydroperoxides and amines. So, we kindly ask to keep it as is.

 

The term Recyclization should be revised. It is very unclear and confusing for me. Probably the terms of “oxycarbenium rearrangement” or “oxycarbenium metathesis” seems more appropriated?

Response: The term “recyclization” was replaced by “cyclic peroxide rearrangement via oxy- or peroxycarbenium ions”.

 

-Be careful to not flip molecules from starting material to final product, that makes the reading more difficult.

Response: Corrected

 

-Take care about too light color for Sulfur or Phosphorous atoms

Response: Corrected

 

-In introduction, about bibliography, a recent review seems missing:

 DOI: 10.1016/bs.aihch.2021.03.001

Response: The article was cited as the reference 88.

Reviewer 2 Report

Comments and Suggestions for Authors

Manuscript Number: chemistry-3227781
Entitled: Macrocyclic organic peroxides: Constructing Medium and Large Cycles with O-O Bonds

This is an interesting scientific study. Therefore, the manuscript is suitable for Chemistry after considering the below comments:

1.      Please expand on the abbreviations in the article in the separate Abbreviations section.

2.      I tried to use the Keywords provided by the Authors in the Scopus database, but they did not allow me to find the works in question. Please suggest other additional Keywords.

 

3.      I have noticed in the Scopus database and other sources that this topic has a very narrow focus among researchers. I would suggest that some information related to the durability (thermal resistance) of the compounds under discussion be included in the introduction. Maybe the relation of the amount of oxygen to the total mass of the compounds.

Author Response

Reviewer 2

This is an interesting scientific study. Therefore, the manuscript is suitable for Chemistry after considering the below comments:

1. Please expand on the abbreviations in the article in the separate Abbreviations section.

Response: The abbreviation list was added after Conclusions section.

 

2. I tried to use the Keywords provided by the Authors in the Scopus database, but they did not allow me to find the works in question. Please suggest other additional Keywords.

Response: The keywords were revised and modified.

 

3.I have noticed in the Scopus database and other sources that this topic has a very narrow focus among researchers. I would suggest that some information related to the durability (thermal resistance) of the compounds under discussion be included in the introduction. Maybe the relation of the amount of oxygen to the total mass of the compounds.

Response: Thanks for the suggestion. Indeed, the thermal stability can vary a lot depending on the peroxide cycle. We have added an overview of the melting point data of the discussed cyclic peroxides to Scheme 2. 

Reviewer 3 Report

Comments and Suggestions for Authors

The review received for evaluation with the aim of publication in Chemistry journal deals with macrocyclic peroxides and has as main author A. Terentev.

At the first sight the work is well done and might be of high interest for chemistry working scientist, mainly in synthetic domain, but not only. This is a beautiful chemistry work,  the review is very well developed, containing 26 pages, 46 schemes and 133 references. 

Introduction is citing 89 references, Scheme 2 is very representative and might be developed further. The chapter about strategies to develop macrocyclic peroxides is divided into several parts, according to this scheme. The main text of the manuscript ends with conclusions, followed by references, written in the correct format.

Although can be published as it is, I can recommend some small improvements:

-Abstract can be a little more expanded, this will be helpful for searching purposes and better representation;

-in scheme 17 CH3CN is written on two rows, please correct.

I would also suggest the authors when they deal with such amount of data and abbreviations, to use either at the end or even at beginning of the text a table/list of abbreviation, will be much easier for readers to follow the text, as not all the chemist are familiarized with all types of chemicals.

At the end, I surely highly recommend this work for publication, as a review is very useful. 

Author Response

Reviewer 3

The review received for evaluation with the aim of publication in Chemistry journal deals with macrocyclic peroxides and has as main author A. Terentev.

At the first sight the work is well done and might be of high interest for chemistry working scientist, mainly in synthetic domain, but not only. This is a beautiful chemistry work, the review is very well developed, containing 26 pages, 46 schemes and 133 references. 

Introduction is citing 89 references, Scheme 2 is very representative and might be developed further. The chapter about strategies to develop macrocyclic peroxides is divided into several parts, according to this scheme. The main text of the manuscript ends with conclusions, followed by references, written in the correct format.

Although can be published as it is, I can recommend some small improvements:

-Abstract can be a little more expanded, this will be helpful for searching purposes and better representation;

Response: Abstract was revised.

 

-in scheme 17 CH3CN is written on two rows, please correct.

Response: Corrected.

 

I would also suggest the authors when they deal with such amount of data and abbreviations, to use either at the end or even at beginning of the text a table/list of abbreviation, will be much easier for readers to follow the text, as not all the chemist are familiarized with all types of chemicals.

Response: The abbreviation list was added after Conclusions section.

 

At the end, I surely highly recommend this work for publication, as a review is very useful. 

Response: We are grateful to the reviewer for the kind words.

Round 2

Reviewer 2 Report

Comments and Suggestions for Authors

The authors conducted important data. This is an interesting paper. The present version of the manuscript is very well developed. The data presented are new and relevant. The present version is much better; therefore, the manuscript is suitable for publication in its current form.

I am only sorry that the Authors made a mistake in "Scheme 36. Probable mechanism of peroxide 90a formation." It is impossible to get a B cation when a proton is removed from the neutral structure of 90a.

Author Response

Comment: I am only sorry that the Authors made a mistake in "Scheme 36. Probable mechanism of peroxide 90a formation." It is impossible to get a B cation when a proton is removed from the neutral structure of 90a.

Response: Thanks for comment. A proton is removed from cation B. Scheme 36 was revised.