Advances in Catalytic C–F Bond Activation and Transformation of Aromatic Fluorides
Round 1
Reviewer 1 Report
Activation of the C-F bond has always been an academic hot and challenge, due to its high polarity and the highest bond energy in organic. In this work, the activation and transformation of the C-F bond in fluoro-aromatics from metal or metal-free systems are summarized in this mini-review by the author. Effective and selective processes and systems have been remarkably mentioned in this review not only in the synthetic methodologies but also in novel fluorinate organic compounds. Therefore, this reviewer would like to recommend this manuscript be published on catalysts.
Author Response
Answers to reviewer 1:
Dear referee,
Thank you very much for your kind comments, and we are delighted to have your recommendation to contribute our work to the Catalysts journal.
Author Response File: Author Response.pdf
Reviewer 2 Report
This is a short and useful review of some recent developments in the field of C(sp2)-F bond functionalization both involving catalysis by transition metal complexes and transition metals-free. I have a few minor notes mentioned below. In addition, the authors’ use of the English language needs some improvement. Overall, I support acceptance after minor revisions.
1) P. 6. Line 196: “heterogeneous cleavage” should be replaced with “heterolytic cleavage”.
2) P. 9, line 270: “partially fluoro-aromatics” should be replaced. A “partially fluorinated aromatics” might a suitable replacement.
3) A general comment. In any review, and this one is not an exception, it is very important to provide readers with sufficient detail to save their valuable time. As such, on Scheme 2.17 please provide structure for BDP ligand (1,2-bis(diphenylphosphino)benzene?).
Similar modifications may be needed on other Schemes.
E.g., on Scheme 2.18 please provide a structure for BDIAlH2.
4) P. 9, line 291: I cannot agree with the statement “ inexpensive Rh-complexes”. Current Rh prices are about $13,000 per troy ounce! Please edit.
5) P. 12, line 401: “arylalkyne” would be a wrong term for intermediate II (Scheme 3.4). Please edit.
6) Scheme 3.4: a reaction leading from a fluoroarene to an intermediate II is implausible. Please correct.
7) Scheme 3.11: please provide a full structure for the fragment “B”.
8) Scheme 3.15, top: the first reaction here does not produce any fluoroarene which is a reagent used at the next step. As such, this reagent should be placed above a reaction arrow leading to the C-N coupled product.
9) The Conclusions and outlook section looks weak. No in-depth analysis is provided. I would prefer seeing this section fully re-written.
Author Response
Please see the attachment.
Author Response File: Author Response.pdf
Reviewer 3 Report
In this review, Xin et al. describe the recent advances in catalytic C-F bond activation and transformation of aromatic fluorides. In my view, the literature presented in this review is sufficient to warrant publication in Catalysts. However, in view of this referee, the technical quality of the review has to be significantly improved prior to publication. In the following, I will mention just a few of the numerous flaws and inconsistencies I noted:
1) Molar ratio of the reactants is not mentioned in many schemes to discuss the product formation (lines 162-173).
2) Please correct the typographical error (line 273, page 9).
3) All schemes are not uniform. The TOF is missing for most of the catalysts.
4) Please replace the word “environmentally beginning” with “environmentally benign” in line 360, page 11.
5) Authors did not discuss any FLP-based C-F bond activation. Is there any reason?
Author Response
Please see the attachment.
Author Response File: Author Response.pdf