Recommendation: Publish after minor revisions noted.
Comments to the Author:
This is an interesting paper worthy of publication in Organic Letters. It describes an original and efficient a photoredox protocol for the synthesis of ****. The present work is performed under mild oxidative conditions which show highly compatible with various functional groups. In the presence of over-stoichiometric **, some of substrates could be directly converted to** derivatives with high regioselectivity. The work is thorough and well done and the structure of the product 5a is further confirmed by X-ray. However, the authors are requested to revise their manuscript by considering the following points.
1) Scheme 2, the yield of B-d2 should be given.
2) In the mechanism, it is not so logical that radical 10 is trapped by ** to release ***. Radical 10 is probably SET reduced by excited Ru* to form an enolated anion, followed by protonation to give product 11. Generally, the SET reduction of*** by photocatalyst will genereate**radical, which could be further reduced to **.
3) ***were proposed as the key intermediated based on the result of two control experiments. I would suggest the authors to do another control experiment, using isolated compound 11 under standard condition to check whether it could be converted to furan or not. Radical 10 could isomerize to an*** radical, which undergoes an intramolecular cycloaddition to form intermediate 14 directly.
4) Table 1, it would be better if the authors could perform the control experiments after the optimized conditions were confirmed.
5) There are also some typos in the manuscript, such as scheme 1c, “ROH”, and table 1, “R= X= H” (“X” should be “CH”).
Additional Questions:
Are there elements of novelty and urgency that warrant rapid communication of the work?: Yes
Is the scope / significance appropriate for the readership of Organic Letters?: Yes
If portions of the work have been previously reported, does the present manuscript represent a substantial extension of the work rather than a fragmentary increment?: No
Does this work represent a logical extension of related studies that is better suited for a full article?: No
Are the experimental results adequately documented and is sufficient detail provided to allow reproduction of the work?: Yes
Is adequate characterization provided for representative compounds with regard to identity and purity?: Yes
Are the literature references appropriate and correct?: Yes
Rate the overall importance of this paper to the field of organic chemistry (10 - High Importance / 1 - Low Importance): 8
Reviewer: 2
Recommendation: The manuscript does not meet the requirements of urgency and novelty that justify publication as a Communication.
Comments to the Author:
The manuscript by ** and coworkers reports on a photochemical synthesis of ***. The reaction is of relatively broad scope, although certain arene substitution is helpful. In general, it compliments other furane cyclization reactions outlined in Scheme 1. Overall, this is a densely written mansucript with a lot of text information. The synthetic aspects (Tables 2-4) are fine, although the reaction times are very long. This qould require reasoning within the discussion, which is not given. My major concern rests with the mechanistic context from Scheme 2. First, the Scheme is barely visible. Secondly, the mechanistic context is extremely complex. I doubt that the postulated cycles can stand. Please note that reaction time sin the range of several days do not coincide with such a complex scenario. The authors should at least demonstrate that some isolated intermediates can be submitted to the main reaction without problem. As to other points, I do not understand the rationlization of the role of**as a base. For example, at stage 9, ** should rather add to the intermediate benzylic cation than inducing an elimination. Compound 11 is deconjugated; the corresponding isomerization to an**intermediate should be preferred, particularly under visible light conditions. Two photocatalytic cycles are not closed throughout the Scheme 2 (steps from 11 to 12 and 15 to 2a). The subsequent SET do not oxidize Ru back – what are the mechanisms closing the cycles?
The review by Krause (Chem Rev 2011, 111, 1994) should be added to the introduction. Generally, the authors omit most of the reviews on general reactivity in the fields of furane cyclization and photochemistry. An update would be required.
In the SI, mp and IR are missing for all new compounds. 19F NMR data should be included, where applicable.
Overall, this is an interesting transformation, but the mechanistic section is far too preliminary. I suggest expanding the work to full paper and include control experiments to arrive at reliable mechanistic insight.
Additional Questions:
Are there elements of novelty and urgency that warrant rapid communication of the work?: No
Is the scope / significance appropriate for the readership of Organic Letters?: Yes
If portions of the work have been previously reported, does the present manuscript represent a substantial extension of the work rather than a fragmentary increment?:
Does this work represent a logical extension of related studies that is better suited for a full article?: Yes
Are the experimental results adequately documented and is sufficient detail provided to allow reproduction of the work?: Yes
Is adequate characterization provided for representative compounds with regard to identity and purity?: No
Are the literature references appropriate and correct?: No
Rate the overall importance of this paper to the field of organic chemistry (10 - High Importance / 1 - Low Importance): 6
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这是两个审稿人的回复
Reviewer: 1
Recommendation: Publish after minor revisions noted.
Comments to the Author:
This is an interesting paper worthy of publication in Organic Letters. It describes an original and efficient a photoredox protocol for the synthesis of ****. The present work is performed under mild oxidative conditions which show highly compatible with various functional groups. In the presence of over-stoichiometric **, some of substrates could be directly converted to** derivatives with high regioselectivity. The work is thorough and well done and the structure of the product 5a is further confirmed by X-ray. However, the authors are requested to revise their manuscript by considering the following points.
1) Scheme 2, the yield of B-d2 should be given.
2) In the mechanism, it is not so logical that radical 10 is trapped by ** to release ***. Radical 10 is probably SET reduced by excited Ru* to form an enolated anion, followed by protonation to give product 11. Generally, the SET reduction of*** by photocatalyst will genereate**radical, which could be further reduced to **.
3) ***were proposed as the key intermediated based on the result of two control experiments. I would suggest the authors to do another control experiment, using isolated compound 11 under standard condition to check whether it could be converted to furan or not. Radical 10 could isomerize to an*** radical, which undergoes an intramolecular cycloaddition to form intermediate 14 directly.
4) Table 1, it would be better if the authors could perform the control experiments after the optimized conditions were confirmed.
5) There are also some typos in the manuscript, such as scheme 1c, “ROH”, and table 1, “R= X= H” (“X” should be “CH”).
Additional Questions:
Are there elements of novelty and urgency that warrant rapid communication of the work?: Yes
Is the scope / significance appropriate for the readership of Organic Letters?: Yes
If portions of the work have been previously reported, does the present manuscript represent a substantial extension of the work rather than a fragmentary increment?: No
Does this work represent a logical extension of related studies that is better suited for a full article?: No
Are the experimental results adequately documented and is sufficient detail provided to allow reproduction of the work?: Yes
Is adequate characterization provided for representative compounds with regard to identity and purity?: Yes
Are the literature references appropriate and correct?: Yes
Rate the overall importance of this paper to the field of organic chemistry (10 - High Importance / 1 - Low Importance): 8
Reviewer: 2
Recommendation: The manuscript does not meet the requirements of urgency and novelty that justify publication as a Communication.
Comments to the Author:
The manuscript by ** and coworkers reports on a photochemical synthesis of ***. The reaction is of relatively broad scope, although certain arene substitution is helpful. In general, it compliments other furane cyclization reactions outlined in Scheme 1. Overall, this is a densely written mansucript with a lot of text information. The synthetic aspects (Tables 2-4) are fine, although the reaction times are very long. This qould require reasoning within the discussion, which is not given. My major concern rests with the mechanistic context from Scheme 2. First, the Scheme is barely visible. Secondly, the mechanistic context is extremely complex. I doubt that the postulated cycles can stand. Please note that reaction time sin the range of several days do not coincide with such a complex scenario. The authors should at least demonstrate that some isolated intermediates can be submitted to the main reaction without problem. As to other points, I do not understand the rationlization of the role of**as a base. For example, at stage 9, ** should rather add to the intermediate benzylic cation than inducing an elimination. Compound 11 is deconjugated; the corresponding isomerization to an**intermediate should be preferred, particularly under visible light conditions. Two photocatalytic cycles are not closed throughout the Scheme 2 (steps from 11 to 12 and 15 to 2a). The subsequent SET do not oxidize Ru back – what are the mechanisms closing the cycles?
The review by Krause (Chem Rev 2011, 111, 1994) should be added to the introduction. Generally, the authors omit most of the reviews on general reactivity in the fields of furane cyclization and photochemistry. An update would be required.
In the SI, mp and IR are missing for all new compounds. 19F NMR data should be included, where applicable.
Overall, this is an interesting transformation, but the mechanistic section is far too preliminary. I suggest expanding the work to full paper and include control experiments to arrive at reliable mechanistic insight.
Additional Questions:
Are there elements of novelty and urgency that warrant rapid communication of the work?: No
Is the scope / significance appropriate for the readership of Organic Letters?: Yes
If portions of the work have been previously reported, does the present manuscript represent a substantial extension of the work rather than a fragmentary increment?:
Does this work represent a logical extension of related studies that is better suited for a full article?: Yes
Are the experimental results adequately documented and is sufficient detail provided to allow reproduction of the work?: Yes
Is adequate characterization provided for representative compounds with regard to identity and purity?: No
Are the literature references appropriate and correct?: No
Rate the overall importance of this paper to the field of organic chemistry (10 - High Importance / 1 - Low Importance): 6
不打算重投OL了 请看看投欧洲化学怎么样，希望大不大
，
楼上的，是哪个副主编管的呢？？