Journal of Organic Chemistry, volume 86, issue 11, pages 7439-7449
Aldol Condensation Versus Superbase-Catalyzed Addition of Ketones to Acetylenes: A Quantum-Chemical and Experimental Study
Publication type: Journal Article
Publication date: 2021-05-20
Journal:
Journal of Organic Chemistry
Quartile SCImago
Q1
Quartile WOS
Q1
Impact factor: 3.6
ISSN: 00223263, 15206904
Organic Chemistry
Abstract
The mechanism of aldol condensation of ketones in KOH/DMSO superbasic media has been investigated using the B2PLYP(D2)/6-311+G**//B3LYP/6-31+G* quantum-chemical approach. It is found that the interaction of three ketone molecules resulting in the formation of the cyclohex-2-enone structure [isophorone or 3,5-dicyclohexyl-5-methylspiro(5.5)undec-2-en-1-one] is thermodynamically more favorable than the interaction of two, three, or four molecules of ketone, resulting in the formation of linear products of the condensation. The formation of the condensation products with the isophorone skeleton can significantly hinder the cascade reactions of ketones with acetylenes [to afford 6,8-dioxabicyclo(3.2.1)octanes or acylcyclopentenols] promoted by superbases. In particular, the kinetically more preferable reactions of autovinylation of 2-methyl-3-butyn-2-ol and autocondensation of acetone are the reasons why interaction of acetone with acetylene does not lead to the products of the cascade assemblies. The predominant formation of the products of these side reactions is confirmed experimentally.
Citations by journals
|
1
2
|
|
|
Physical Chemistry Chemical Physics
|
Physical Chemistry Chemical Physics
2 publications, 33.33%
|
|
Encyclopedia
|
Encyclopedia
1 publication, 16.67%
|
|
Doklady Chemistry
|
Doklady Chemistry
1 publication, 16.67%
|
|
Journal of Molecular Liquids
|
Journal of Molecular Liquids
1 publication, 16.67%
|
|
Organic Letters
|
Organic Letters
1 publication, 16.67%
|
|
1
2
|
Citations by publishers
|
1
2
|
|
|
Royal Society of Chemistry (RSC)
|
Royal Society of Chemistry (RSC)
2 publications, 33.33%
|
|
Multidisciplinary Digital Publishing Institute (MDPI)
|
Multidisciplinary Digital Publishing Institute (MDPI)
1 publication, 16.67%
|
|
Pleiades Publishing
|
Pleiades Publishing
1 publication, 16.67%
|
|
Elsevier
|
Elsevier
1 publication, 16.67%
|
|
American Chemical Society (ACS)
|
American Chemical Society (ACS)
1 publication, 16.67%
|
|
1
2
|
- We do not take into account publications that without a DOI.
- Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
- Statistics recalculated weekly.
{"yearsCitations":{"type":"bar","data":{"show":true,"labels":[2021,2022,2023],"ids":[0,0,0],"codes":[0,0,0],"imageUrls":["","",""],"datasets":[{"label":"Citations number","data":[1,1,4],"backgroundColor":["#3B82F6","#3B82F6","#3B82F6"],"percentage":["16.67","16.67","66.67"],"barThickness":null}]},"options":{"indexAxis":"x","maintainAspectRatio":true,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"}},"x":{"ticks":{"stepSize":1,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"}}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Citations per year","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}},"journals":{"type":"bar","data":{"show":true,"labels":["Physical Chemistry Chemical Physics","Encyclopedia","Doklady Chemistry","Journal of Molecular Liquids","Organic Letters"],"ids":[1773,27647,11308,13597,3315],"codes":[0,0,0,0,0],"imageUrls":["\/storage\/images\/resized\/leiAYcRDGTSl5B1eCnwpSGqmDEUEfDPPoYisFGhT_medium.webp","\/storage\/images\/resized\/MjH1ITP7lMYGxeqUZfkt2BnVLgjkk413jwBV97XX_medium.webp","\/storage\/images\/resized\/oZgeErrVFhuDksyqFURLvYS1wtVSBWczh001igGo_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp"],"datasets":[{"label":"","data":[2,1,1,1,1],"backgroundColor":["#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6"],"percentage":[33.33,16.67,16.67,16.67,16.67],"barThickness":13}]},"options":{"indexAxis":"y","maintainAspectRatio":false,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"}},"x":{"ticks":{"stepSize":null,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"}}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Journals","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}},"publishers":{"type":"bar","data":{"show":true,"labels":["Royal Society of Chemistry (RSC)","Multidisciplinary Digital Publishing Institute (MDPI)","Pleiades Publishing","Elsevier","American Chemical Society (ACS)"],"ids":[123,202,101,17,40],"codes":[0,0,0,0,0],"imageUrls":["\/storage\/images\/resized\/leiAYcRDGTSl5B1eCnwpSGqmDEUEfDPPoYisFGhT_medium.webp","\/storage\/images\/resized\/MjH1ITP7lMYGxeqUZfkt2BnVLgjkk413jwBV97XX_medium.webp","\/storage\/images\/resized\/oZgeErrVFhuDksyqFURLvYS1wtVSBWczh001igGo_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp"],"datasets":[{"label":"","data":[2,1,1,1,1],"backgroundColor":["#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6"],"percentage":[33.33,16.67,16.67,16.67,16.67],"barThickness":13}]},"options":{"indexAxis":"y","maintainAspectRatio":false,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"}},"x":{"ticks":{"stepSize":null,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"}}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Publishers","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}}}
Metrics
Cite this
GOST |
RIS |
BibTex |
MLA
Cite this
GOST
Copy
Orel V. B. et al. Aldol Condensation Versus Superbase-Catalyzed Addition of Ketones to Acetylenes: A Quantum-Chemical and Experimental Study // Journal of Organic Chemistry. 2021. Vol. 86. No. 11. pp. 7439-7449.
GOST all authors (up to 50)
Copy
Orel V. B., Vitkovskaya N., Bobkov A. S., Semenova N. V., Schmidt E. Yu., Trofimov B. A. Aldol Condensation Versus Superbase-Catalyzed Addition of Ketones to Acetylenes: A Quantum-Chemical and Experimental Study // Journal of Organic Chemistry. 2021. Vol. 86. No. 11. pp. 7439-7449.
Cite this
RIS
Copy
TY - JOUR
DO - 10.1021/acs.joc.1c00388
UR - https://doi.org/10.1021%2Facs.joc.1c00388
TI - Aldol Condensation Versus Superbase-Catalyzed Addition of Ketones to Acetylenes: A Quantum-Chemical and Experimental Study
T2 - Journal of Organic Chemistry
AU - Orel, Vladimir B
AU - Vitkovskaya, Nadezhda
AU - Bobkov, A. S.
AU - Trofimov, B. A.
AU - Semenova, N. V.
AU - Schmidt, Elena Yu
PY - 2021
DA - 2021/05/20 00:00:00
PB - American Chemical Society (ACS)
SP - 7439-7449
IS - 11
VL - 86
SN - 0022-3263
SN - 1520-6904
ER -
Cite this
BibTex
Copy
@article{2021_Orel,
author = {Vladimir B Orel and Nadezhda Vitkovskaya and A. S. Bobkov and B. A. Trofimov and N. V. Semenova and Elena Yu Schmidt},
title = {Aldol Condensation Versus Superbase-Catalyzed Addition of Ketones to Acetylenes: A Quantum-Chemical and Experimental Study},
journal = {Journal of Organic Chemistry},
year = {2021},
volume = {86},
publisher = {American Chemical Society (ACS)},
month = {may},
url = {https://doi.org/10.1021%2Facs.joc.1c00388},
number = {11},
pages = {7439--7449},
doi = {10.1021/acs.joc.1c00388}
}
Cite this
MLA
Copy
Orel, Vladimir B., et al. “Aldol Condensation Versus Superbase-Catalyzed Addition of Ketones to Acetylenes: A Quantum-Chemical and Experimental Study.” Journal of Organic Chemistry, vol. 86, no. 11, May. 2021, pp. 7439-7449. https://doi.org/10.1021%2Facs.joc.1c00388.