Monday, April 12, 2010 10:08 AM
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04-Dec-2009
Dr. Rainer Glaser
Department of Chemistry
University of Missouri-Columbia
321 Chemistry Building
Columbia, Missouri, 65211
United States
Phone: (573) 882 0331
Fax: (573) 882 2754
Email: glaserr@missouri.edu
RE: The Journal of Organic Chemistry
Manuscript ID: jo-2009-02358c
Title: "Asymmetry in the N-Inversion of Heteroarene Imines: Pyrimidin-4(3H)-Imine,
Pyridin-2(1H)-Imine, and 1H-Purine-6(9H)-Imine"
Author(s): Glaser, Rainer; Yin, Jian; Miller, Stephanie
Dear Rainer:
Thank you for submitting your manuscript for publication in The Journal of Organic
Chemistry (JOC). Your manuscript has been examined with the assistance of two
expert reviewers who have evaluated its scientific merit and potential for interest
to the readership of the JOC. I have also reviewed your manuscript in my office in
light of their comments which are attached. On balance this assessment is positive
although some revisions are recommended. I am pleased to invite you to submit a
revised manuscript that addresses the concerns raised by the reviewers.
To expedite processing, please explicitly address the issues raised by the
reviewers in your cover letter, and indicate the changes that have been made. If
you decide not to make some of the changes suggested by the reviewers, please
explain the reason why you think each of those suggested changes should not be
made.
Please use the text box provided in the “Response to Decision Letter” section of
the revision submission Web form to indicate your detailed responses to all of the
points raised by the reviewers. You also have the option of providing an attached
file with the detailed responses.
Per our Guidelines for Authors, “if the revised manuscript is not returned to the
Editor within 45 days after the revision is requested, and the author has not made
alternative arrangements with the Editor for completion of the manuscript, the
manuscript will be deactivated”. We hope to see your revised manuscript before
January 18, 2010.
Other changes we would like you to make on your manuscript follow, along with
instructions for submitting your revision. I look forward to receiving your revised
manuscript.
With sincere regards,
Bob
Robert J. McMahon
Associate Editor
The Journal of Organic Chemistry
Phone: 608-263-5548
Page 1 of 4
FAX: 877-389-1955 or 608-263-5549 (int.)
Email: joc@chem.wisc.edu
The following items need to be addressed in your revision:
1.Please provide a Table of Contents for the Supporting Information.
To submit your revised manuscript: log into ACS Paragon Plus at http://
pargonplus.acs.org/login and select “My Authoring Activity”. There you will find
your manuscript title listed under “Revision Requested by Editorial Office”. Your
original files are available to you when you upload your revised manuscript. If you
are replacing files, please remove the old version of the file from the manuscript
before uploading the new file.
------------------------------------
Reviewer(s)' Comments to Author:
Reviewer: 1
Recommendation: Publish in The Journal of Organic Chemistry after minor revisions.
Comments:
Review attached
Additional Questions:
Significance: Top 10%
Interest to The Journal of Organic Chemistry readership: Above Average
Scholarly analysis/presentation: Top 10%
Are the conclusions adequately supported by the data?: Yes
Are the literature references appropriate and correct?: Yes
Are the compounds reported adequately characterized with regard to identity and
purity?: Yes
Reviewer: 2
Recommendation: Publish in The Journal of Organic Chemistry after minor revisions.
Comments:
This paper presents an interesting, valuable and very careful ab initio theoretical
study on the E-Z isomerization of three heteroaromatic compounds containing an
amidine substructure with an exocyclic imino group. The high level calculations use
the perturbational MP2(full)-level and coupled cluster theory of the CCSD level
with reasonably large basis sets including polarization functions for stationary
states and relevant parts of the potential energy surfaces. In addition
thermochemical data for E- and Z-isomers and transition states have been evaluated
at the CCSD(T) level with two larger basis sets. E-isomers are energetically
preferred in a larger extend for the purine compound due to an additional internal
hydrogen bond. Transition states for inversion are not colinear but refer to
entiomeric non-linear forms with hydrogen and nitrogen displaced perpendicularly
out of the ring-plane in different directions. An observed asymmetry in the Ninversion path has been studied by consideration of additional bonding overlap in
the HOMO. These before presented gas phase data have been extended to solution
states for halogen-bonded aggregates.
Page 2 of 4
Results are presented with sufficient details in tables and figures and clearly
discussed and interpreted. The MS should be accepted with the following minor corrections:
p. 7, line 50: What does a.k.a. mean?
p. 11, heading of Table 3: Subscript b is missing.
p. 12, Scheme 3: Could one indicate in the plot the orientation of the used
coordinates?
p. 15, line 21: In Fig. 4 are no numbers in parentheses given.
p. 17, Fig. 6: The description is not easy to understand. Instead of colors,
numbers or letters should be given in the plot. (My printer shows no golden curve.)
What present the lower curves (those without dots)?
Additional Questions:
Significance: Above Average
Interest to The Journal of Organic Chemistry readership: Above Average
Scholarly analysis/presentation: Top 10%
Are the conclusions adequately supported by the data?: Yes
Are the literature references appropriate and correct?: Yes
Are the compounds reported adequately characterized with regard to identity and
purity?: Yes
---------------------------------------
If you encounter any difficulties with the online submission process, please
contact the ACS Help Desk at paragonplus@acs.org, 800-227-9919 (USA/Canada), or
202-872-4357 (outside of USA/Canada).
Page 3 of 4
Review of:
The Journal of Organic Chemistry Manuscript ID : jo-2009-02358c
Title : "Asymmetry in the N-Inversion of Heteroarene Imines: Pyrimidin-4(3H)Imine, Pyridin-2(1H)-Imine, and 1H-Purine-6(9H)-Imine"
Author(s): Glaser, Rainer; Yin, Jian; Miller, Stephanie
Specific Comments:
Abstract: It might be a good idea to define “SOSP” here or at its first mention in
the text.
Table 2: Why are the “best estimates” lower than all of the tabulated energies?
It seems that these are delta G (not delta E) and should be noted as such.
Page 7: “extra stabilization” (two words”)
Page 11: Should “equally” be removed here?
Table 3: What is the significance of the asterisk and why is alpha equal to 180°?
A table footnote is warranted here.
Pages 13-15: I am not sure that the sentence that spans these pages is a
sentence. Is word missing?
Page 15: “representing” (not “represent”)
Page 15: “motif” (not “motive”)
Page 25: Somehow (maybe a font issue), a classic division symbol has
appeared on this page three times.
Page 25: “points out” (not “points up”)
Page 26: “studied; that is” (semicolon here)
References: The article titles are nice, but probably not allowed.
General Comments:
This is a very well-written paper that is also fairly lucid, given the complexity of
the subject. The authors have established that the transition state for E/Z imine
isomerization is asymmetric (non-planar). This is the key finding that elevates
this manuscript to a high level and should make it of fairly broad interest to a
variety of physical organic chemists. Table 3 reports the angle alpha computed
for the transition structure. These are all significantly less than the “intuitive”
value of 180° (except for the * data set, which needs further comment)—going as
low as 133°! Figure 5 nicely shows the difference between the “intuitive” and
found energies along the isomerization pathway. The molecular orbital
explanation is satisfying and illustrates the more-bonding-in-the-transition-stateis-better principle.
I support publication of this manuscript in the Journal of Organic Chemistry
following attention to aforementioned points.
Dr. Rainer Glaser
Professor in Chemistry
Telephone: (573) 882-0331
Facsimile: (573) 882-2754
E-Mail: GlaserR@missouri.edu
WWW: http://web.missouri.edu/~glaserr
Department of Chemistry
University of Missouri–Columbia
321 Chemistry Building
601 South College Avenue
Columbia, Missouri 65211
USA
January 4, 2010
Professor Robert J. McMahon, Associate Editor
The Journal of Organic Chemistry
RE: jo‐2009‐02358c - Revised
Asymmetry in the N-Inversion of Heteroarene Imines: Pyrimidin-4(3H)-Imine, Pyridin2(1H)-Imine, and 1H-Purine-6(9H)-Imine
By Rainer Glaser,* Jian Yin, and Stephanie Miller
Dear Bob:
Thank you very much for your letter of December 4, 2009, regarding the above cited manuscript. We
are delighted that the paper was well received by the reviewers and we very much appreciate their
careful reading of the manuscript. We have now prepared a revision and the changes made in response
to the reviewers’ comments are as follows.
Response to Reviewer 1:
[1.1] The abbreviation “a.k.a.” stands for “also known as” and was used on p. 3 and p. 7. We can do
without the term and the term has been omitted in the revision.
[1.2] Table 3: Superscripts “a” and “b” now appear in the heading.
[1.3] Scheme 3: Added axes as requested and also labeled the minima.
[1.4] The “numbers in parentheses” mentioned in the text were missing in Fig. 4 and they have now
been added.
[1.5] Figs. 5 and 6: Labels were added to the curves in both figures. The three curves shown without
markers in Fig. 6 are the curves of Fig. 5 and they are shown again for reference in Fig. 6.
Response to Reviewer 2:
[2.1] Abstract: Added “… and stationary structures for in-plane N-inversion corresponds to secondorder saddle points (SOSP) on the potential energy surface.” With this addition, “SOSP” is now
defined.
[2.2] The “best estimates” are ΔG values. Since ΔE(MP2) > ΔG(MP2) (thermochemistry reduces
barriers) and considering that ΔE(best level) < ΔE(MP2), it follows that ΔG(best level) < ΔG(MP2).
[2.3] P. 7, last line: Corrected spelling of “extra stabilization”.
[2.4] P. 11: Yes, “equally” was dropped and “either” was added at the end of the sentence.
[2.5] Table 3: The special level dependency of the PUI transition state structure is discussed in the text
(in some detail), the “*” is not really needed in Table 3, and the mark was omitted in revision.
[2.6] Replaced “that” by “at the” in the sentence that starts on the bottom of p. 13 and continues on top
of p. 15: “The “best estimates” in Table 2 are based on energies computed at the levels CC-L4 (PMI,
PYI) and CC-L4’ (PUI) and thermodynamic parameters computed at the MP2(full)/6-31G(d) level.”
[2.7] P. 15: “… representing less polar regions.”
[2.8] P. 15: Corrected spelling of “motif”.
[2.9] P. 25: Replaced “÷” by “-” (three instances).
[2.10] P. 25: Replaced “points up” by “points out”.
[2.11] While JOC does not require article titles, I don’t know whether there is a rule that says that JOC
does not allow article titles. Of course, if JOC does not allow titles, the titles should be deleted and I can
do that or the Journals Department could do that. On the other hand, if titles are allowed, I’d rather keep
them.
Additional Changes
[A.1] Table of Contents added to Supporting Information.
[A.2] Scheme 1: Corrected stereochemical label of (E)-PUI.
I believe we have addressed all of the reviewer comments and we hope that the paper is now in good
shape for publication.
All the Very Best in 2010!
With Best Regards,
Rainer
Monday, April 12, 2010 10:04 AM
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11-Jan-2010
RE: The Journal of Organic Chemistry
Manuscript ID: jo-2009-02358c.R1
Title: "Asymmetry in the N-Inversion of Heteroarene Imines: Pyrimidin-4(3H)-Imine,
Pyridin-2(1H)-Imine, and 1H-Purine-6(9H)-Imine"
Author(s): Glaser, Rainer; Yin, Jian; Miller, Stephanie
Dear Rainer:
I am pleased to inform you that your manuscript has been accepted for publication
in The Journal of Organic Chemistry. Your manuscript has been forwarded to the ACS
Publications office.
You will be contacted in the near future by the ACS Journal Publishing Staff
regarding the page proofs for your manuscript. After you approve your page proofs,
your manuscript will be published on the Web in approximately 48 hours. In view of
this rapid publication time, it is important to review your page proofs carefully.
Once a manuscript appears on the Web it is considered published. Any change to the
manuscript will then need to be submitted to the EIC journal office as an addition
or correction.
Thank you again for choosing The Journal of Organic Chemistry for the publication
of your work.
With sincere regards,
Bob
Robert J. McMahon Associate Editor The Journal of Organic Chemistry Phone: 608-263-5548 Fax: 877-389-1955 or 608-263-5549 (Int.) Email: joc@chem.wisc.edu
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