Catalytic Efficiency of Primary α-Amino Amides as Multifunctional Organocatalysts in Recent Asymmetric Organic Transformations
Round 1
Reviewer 1 Report
Manuscript ”Catalytic Efficiency of Primary a-Amino Amides as Multifunctional Organocatalysts in Recent Asymmetric Organic Transformations“, authors: U. V. Subba Reddy, B. Anusha, Z. Begum, C. Seki, Y. Okuyama, M. Tokiwa, S. Tokiwa, M. Takeshita, H. Nakano; Manuscript ID: catalysts-2024562, submitted to the journal Catalysts.
Since 2009 no review appeared on the use of a-amino carboxamides as organocatalysts in asymmetric organic reactions, accordingly, the publication of this review is timely and well-come. Moreover, even the previous review concentrated mostly on the use of prolinamides as chiral catalysts, thus the publication of this paper would certainly fill a gap. Accordingly, I would like the manuscript to be published, however, there is a very large number of mistakes, typos, incorrect use of some terms and strange phrasings. Thus, I suggest major revision of the manuscript before being published. Some mistakes (including but not limited to these) are listed below:
I think that the authors intended to review reactions catalyzed by amino carboxamides, thus, I suggest they consider the use of carboxamide word instead of amide throughout the manuscript (other amides, such as sulfonamides, phosphoramides are not included).
The use of capital letter in the text is unnecessary (moreover incorrect), i.e. Aldehydes, Aldol reaction, Epoxides, Isatin, etc.; except when the reaction was named after the discoverer (Michael, Strecker, etc). Thus, in the text Strecker was several times given incorrectly (without capital letter).
Line 139, ref 67 is not matching this place.
Scheme 6, I-1 and I-3 are identical (I-3 should be changed).
Scheme 7, the formula of the aldehyde should be more general (with an R substituent) as in the publication. In the text the benzaldehyde name should be replaced with 4-nitrobenzaldehyde.
On page 11 Scheme 13 should precede Scheme 14 in the text.
Page 15 and references, ref 79 is identical with 83.
Scheme 24, re-face (not ri-face).
Page 19, the authors denote the used 1,2-diamine derivatives as C2-asymmetric, in fact they are C2-symmetric if the substituents are identical.
On Scheme 29 some formulae are mistaken (78f, 78g) the configurations show as they were prepared from D-Phe (opposite to the original publication).
Scheme 33, formulae 107 and 108 are incorrect (NH2-s are missing and the phenyl ring are denoted PH).
Line 508, the catalyst 116 was not prepared from L-Phe.
Scheme 37, the formulae 126h is incorrect, please check the stereochemistry.
The organization of the subchapters could be improved. Thus, subchapter 2.5. and 2.8. could be merged, as both describe asymmetric reductions with trichlorosilane (both reported by the same laboratory).
Most importantly, the language usage should be checked in detail and corrected.
Finally, I consider the review valuable, however, the presentation style should be significantly improved, especially as concerns the text.
Author Response
Please see the attachment
Author Response File: 
Author Response.pdf
Reviewer 2 Report
This review article “Catalytic efficiency of primary α-amino amides as multifunctional organocatalysts in recent asymmetric organic transformations” reported a collective of papers focused on reactions catalyzed by chiral primary α-amino amides. Based on the authors’ works in this area, 9 different kinds of catalytic asymmetric reactions were included. As the authors claimed, chiral primary α-amino amides are relatives of less expensive, easy to access, abundant, commercially available chiral resources as catalysts which do and still will play an important role in asymmetric catalytic area. This review is a good conclusion after decades since primary amino amide emerged as chiral catalysts. It is a well-organized, well-written review article with good amount of work. Therefore, the review recommends it to be published on Catalysts after minor revision.
There are some issues that should be addressed.
Keywords: please keep the same formats.
Please define the term “DCM” or use “CH2Cl2” instead.
Page 3, line 110: “-hydroxy carbonyls” should be “β-hydroxy carbonyls”.
Page 4, line 128: “acidic strength” would be better with “acidity”. Scheme 4, please remove the negative charge on N.
Page 5, scheme 5: please revise the product structure. “X” atom is missing. “sym:anti” should be “syn:anti”. The format for diastereoselectivities should keep the same for the whole manuscript.
Page 6, “X” atom is missing for products. Line 184, “Fig. 3” should be “Figure 3”.
Page 7, the structure of product 9 does not correspond with scheme 7.
Page 9, scheme 10: please revise “4Ao MS”.
Page 10, scheme 11: please define “DNP”.
Page 11, scheme 12: please define “4-NMA”. Please depict the yields, ee, and dr.
Page 14, scheme 17: “3 cycles” should not be depicted as reaction conditions. Line 330 and 331: “acetic proton” is very confusing. Please revise.
Page 15, scheme 19: please double check the “R or S”. It’s incorrect. “BoC2O” should be “Boc2O”.
Page 18, line 411 and line 417: “adamantoyl” should be “adamantyl”. Line 419: “selectivity’s” should be “selectivities”. Scheme 28: “Toulene” should be “toluene”.
Page 19, line 433 and line 438: “C1- and C2- asymmetric” should be “C1- and C2- symmetric”. Scheme 29: tittle should include “C1”. Line 439: “78 and 79” should be “79 and 78” with consistent with “C1- and C2- symmetric”.
Page 20, scheme 30: please depict catalyst loading. Please define IPA. IPA is an additive. Please depict its amount used. The same to scheme 32.
Page 21, scheme 32: the chirality of sulfoxide is incorrect.
Page 22, scheme 33: “i-Pr2Et3N” is incorrect.
Page 25, scheme 37: please double check the configuration of 126h.
Page 27, line 592: please define “CILs”.
Author Response
Please see the attachment
Author Response File: Author Response.pdf
Reviewer 3 Report
The paper entitled “Catalytic Efficiency of Primary a-Amino Amides as Multifunctional Organocatalysts in Recent Asymmetric Organic Transformations” constitutes a short review of the synthesis and use as catalysts of the named compounds.
The paper is of interest, and it could be published after minor corrections as follows:
1. The term enantiotropic in line 67 must be changed to enantiotopic.
2. The term optical yields in line 148must be changed to enantioselectivity.
3. The structure of compound 6 in Scheme 5 must be corrected.
4. In Scheme 6, the structure I-1 is the same than I-3, and Ts-1-Ts-3 are not really transition states but binary complexes.
5. The structure of compound 9 in Scheme 7 must be corrected.
After the corresponding corrections the paper could be accepted for publication
Author Response
Please see the attachment
Author Response File: Author Response.pdf
Round 2
Reviewer 1 Report
Revised version of the manuscript ”Catalytic Efficiency of Primary a-Amino Amides as Multifunctional Organocatalysts in Recent Asymmetric Organic Transformations“, authors: U. V. Subba Reddy, B. Anusha, Z. Begum, C. Seki, Y. Okuyama, M. Tokiwa, S. Tokiwa, M. Takeshita, H. Nakano; Manuscript ID: catalysts-2024562-v2, submitted to the journal Catalysts.
Since most of the mistakes and typos were corrected in the revised version of the manuscript, I agree with its publication in the present form. Although, the authors kept separate subsections 2.5. and 2.8., which in my opinion should be merged, I can accept their reasoning (though I still consider it a better choice to merge these subsections). Similarly, the amino amide term was not changed to amino carboxyamides. Although the latter is a more precise denotation of the compounds reviewed, I agree with their opinion that the presently used term is more succinct (though other amides than carboxyamides were not reviewed, thus is not more suitable). Importantly, significant improvements were made in the text. Altogether, I suggest acceptance of the manuscript for publication.
