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DFT Mechanistic Study of the Cyclopropanation of Styrene and Aryldiazodiacetate Catalyzed by Tris(pentafluorophenyl)borane

[Image: see text] Metal-free boron Lewis acids, tris(pentafluorophenyl)borane B(C(6)F(5))(3), have the advantages of low toxicity and low cost and are a promising catalyst. A density functional theory (DFT) calculation was used to clarify the mechanism and the origin of the diastereoselective cyclop...

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Autores principales: Wen, Xiuling, Lu, Peiquan, Shen, Yong, Peng, Haojie, Ke, Zhuofeng, Zhao, Cunyuan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9025995/
https://www.ncbi.nlm.nih.gov/pubmed/35474821
http://dx.doi.org/10.1021/acsomega.2c00200
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author Wen, Xiuling
Lu, Peiquan
Shen, Yong
Peng, Haojie
Ke, Zhuofeng
Zhao, Cunyuan
author_facet Wen, Xiuling
Lu, Peiquan
Shen, Yong
Peng, Haojie
Ke, Zhuofeng
Zhao, Cunyuan
author_sort Wen, Xiuling
collection PubMed
description [Image: see text] Metal-free boron Lewis acids, tris(pentafluorophenyl)borane B(C(6)F(5))(3), have the advantages of low toxicity and low cost and are a promising catalyst. A density functional theory (DFT) calculation was used to clarify the mechanism and the origin of the diastereoselective cyclopropanation of aryldiazodiacetate and styrene derivatives catalyzed by B(C(6)F(5))(3). Four pathways were calculated: B(C(6)F(5))(3)-catalyzed N-, C-, and O-bound boron-activated aryldiazodiacetate and without B(C(6)F(5))(3) catalysis. By calculating and comparing the energy barriers, the most possible reaction mechanism was proposed, that is, first, B(C(6)F(5))(3) catalyzed O-bound boron to activate aryldiazodiacetate, followed by the removal of a N(2) molecule, and finally, styrene nucleophilic attack occurred to produce [2+1] cyclopropane products. N(2) removal is the rate-limiting step, and this step determines the preference of a given mechanism. The calculated results are in agreement with experimental observations. The origin of diastereoselectivity is further explained on the basis of the favorable mechanism. The steric hindrance interference between the styrene aryl group and the large tri(pentafluorophenyl)borane B(C(6)F(5))(3) and the favorable π–π stacking interaction between the benzene rings combined to cause the high diastereoselectivity, which resulted in lower energy of the transition state (TS) corresponding to the reaction mechanism. The calculated results not only provide a more detailed explanation of the mechanism for the experimental study but also have certain reference and guiding significance for other catalytic cyclopropanation reactions.
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spelling pubmed-90259952022-04-25 DFT Mechanistic Study of the Cyclopropanation of Styrene and Aryldiazodiacetate Catalyzed by Tris(pentafluorophenyl)borane Wen, Xiuling Lu, Peiquan Shen, Yong Peng, Haojie Ke, Zhuofeng Zhao, Cunyuan ACS Omega [Image: see text] Metal-free boron Lewis acids, tris(pentafluorophenyl)borane B(C(6)F(5))(3), have the advantages of low toxicity and low cost and are a promising catalyst. A density functional theory (DFT) calculation was used to clarify the mechanism and the origin of the diastereoselective cyclopropanation of aryldiazodiacetate and styrene derivatives catalyzed by B(C(6)F(5))(3). Four pathways were calculated: B(C(6)F(5))(3)-catalyzed N-, C-, and O-bound boron-activated aryldiazodiacetate and without B(C(6)F(5))(3) catalysis. By calculating and comparing the energy barriers, the most possible reaction mechanism was proposed, that is, first, B(C(6)F(5))(3) catalyzed O-bound boron to activate aryldiazodiacetate, followed by the removal of a N(2) molecule, and finally, styrene nucleophilic attack occurred to produce [2+1] cyclopropane products. N(2) removal is the rate-limiting step, and this step determines the preference of a given mechanism. The calculated results are in agreement with experimental observations. The origin of diastereoselectivity is further explained on the basis of the favorable mechanism. The steric hindrance interference between the styrene aryl group and the large tri(pentafluorophenyl)borane B(C(6)F(5))(3) and the favorable π–π stacking interaction between the benzene rings combined to cause the high diastereoselectivity, which resulted in lower energy of the transition state (TS) corresponding to the reaction mechanism. The calculated results not only provide a more detailed explanation of the mechanism for the experimental study but also have certain reference and guiding significance for other catalytic cyclopropanation reactions. American Chemical Society 2022-04-07 /pmc/articles/PMC9025995/ /pubmed/35474821 http://dx.doi.org/10.1021/acsomega.2c00200 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Wen, Xiuling
Lu, Peiquan
Shen, Yong
Peng, Haojie
Ke, Zhuofeng
Zhao, Cunyuan
DFT Mechanistic Study of the Cyclopropanation of Styrene and Aryldiazodiacetate Catalyzed by Tris(pentafluorophenyl)borane
title DFT Mechanistic Study of the Cyclopropanation of Styrene and Aryldiazodiacetate Catalyzed by Tris(pentafluorophenyl)borane
title_full DFT Mechanistic Study of the Cyclopropanation of Styrene and Aryldiazodiacetate Catalyzed by Tris(pentafluorophenyl)borane
title_fullStr DFT Mechanistic Study of the Cyclopropanation of Styrene and Aryldiazodiacetate Catalyzed by Tris(pentafluorophenyl)borane
title_full_unstemmed DFT Mechanistic Study of the Cyclopropanation of Styrene and Aryldiazodiacetate Catalyzed by Tris(pentafluorophenyl)borane
title_short DFT Mechanistic Study of the Cyclopropanation of Styrene and Aryldiazodiacetate Catalyzed by Tris(pentafluorophenyl)borane
title_sort dft mechanistic study of the cyclopropanation of styrene and aryldiazodiacetate catalyzed by tris(pentafluorophenyl)borane
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9025995/
https://www.ncbi.nlm.nih.gov/pubmed/35474821
http://dx.doi.org/10.1021/acsomega.2c00200
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