Understanding the Mechanism and Selectivities of the Reaction of Meta-Chloroperbenzoic Acid and Dibromocarbene with β-Himachalene: A DFT Study
This study was performed to understand the site selectivity in the reaction between β-himachalene and meta-chloroperbenzoic acid (m-CPBA) in the first step followed by the addition of dibromocarbene (CBr2) to the main monoepoxidation product Pα formed in the first reaction. Calculations were perform...
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| Format: | Article |
| Language: | English |
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Wiley
2020-01-01
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| Series: | Heteroatom Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2020/8885991 |
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| author | Sana El Hamidi Malika Khnifira El Mokhtar Lemdek Redouan Hammal Noureddine Barka M’hamed Sadiq Ahmed Benharref Ahmed Chekroun Hssaine Zgou Mohamed Abdennouri |
| author_facet | Sana El Hamidi Malika Khnifira El Mokhtar Lemdek Redouan Hammal Noureddine Barka M’hamed Sadiq Ahmed Benharref Ahmed Chekroun Hssaine Zgou Mohamed Abdennouri |
| author_sort | Sana El Hamidi |
| collection | DOAJ |
| description | This study was performed to understand the site selectivity in the reaction between β-himachalene and meta-chloroperbenzoic acid (m-CPBA) in the first step followed by the addition of dibromocarbene (CBr2) to the main monoepoxidation product Pα formed in the first reaction. Calculations were performed using the Becke three-parameter hybrid exchange functional and the Lee–Yang–Parr correlation functional (B3LYP) with the 6-311 + G (d, p) basis set. Transition states were located by QST2, and their highlighting was validated by the existence of only one imaginary frequency in the Hessian matrix. The action of m-CPBA on β-himachalene was analyzed on the two double bonds of β-himachalene whose theoretical calculations show that the attack affects the most substituted double bond on α side containing hydrogen of ring junction. The obtained Pα product thereafter treated with dibromocarbene leads via an exothermic reaction to the six-membered ring double bond position of α-monoepoxide. The major products Pαα are kinetically and thermodynamically favored with a high stereoselectivity in perfect correlation with the experimental observations. |
| format | Article |
| id | doaj-art-74cfdcf7875143148e3ad073746758d0 |
| institution | Kabale University |
| issn | 1042-7163 1098-1071 |
| language | English |
| publishDate | 2020-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | Heteroatom Chemistry |
| spelling | doaj-art-74cfdcf7875143148e3ad073746758d02025-02-03T05:52:28ZengWileyHeteroatom Chemistry1042-71631098-10712020-01-01202010.1155/2020/88859918885991Understanding the Mechanism and Selectivities of the Reaction of Meta-Chloroperbenzoic Acid and Dibromocarbene with β-Himachalene: A DFT StudySana El Hamidi0Malika Khnifira1El Mokhtar Lemdek2Redouan Hammal3Noureddine Barka4M’hamed Sadiq5Ahmed Benharref6Ahmed Chekroun7Hssaine Zgou8Mohamed Abdennouri9Sultan Moulay Slimane University, Research Group in Environmental Sciences and Applied Materials (SEMA), FP Khouribga, B.P. 145 25000, Khouribga, MoroccoSultan Moulay Slimane University, Research Group in Environmental Sciences and Applied Materials (SEMA), FP Khouribga, B.P. 145 25000, Khouribga, MoroccoSultan Moulay Slimane University, Research Group in Environmental Sciences and Applied Materials (SEMA), FP Khouribga, B.P. 145 25000, Khouribga, MoroccoCadi Ayyad University, Faculty of Sciences Semlalia, Laboratory of Biomolecular Chemistry Natural Substances and Reactivity (URAC 16), BP 2390, Marrakech, MoroccoSultan Moulay Slimane University, Research Group in Environmental Sciences and Applied Materials (SEMA), FP Khouribga, B.P. 145 25000, Khouribga, MoroccoSultan Moulay Slimane University, Research Group in Environmental Sciences and Applied Materials (SEMA), FP Khouribga, B.P. 145 25000, Khouribga, MoroccoCadi Ayyad University, Faculty of Sciences Semlalia, Laboratory of Biomolecular Chemistry Natural Substances and Reactivity (URAC 16), BP 2390, Marrakech, MoroccoCadi Ayyad University, Faculty of Sciences Semlalia, Laboratory of Biomolecular Chemistry Natural Substances and Reactivity (URAC 16), BP 2390, Marrakech, MoroccoIbn Zohr University, Material Sciences, Processes, Environment & Modeling, Polydisciplinary Faculty, Ouarzazate, MoroccoSultan Moulay Slimane University, Research Group in Environmental Sciences and Applied Materials (SEMA), FP Khouribga, B.P. 145 25000, Khouribga, MoroccoThis study was performed to understand the site selectivity in the reaction between β-himachalene and meta-chloroperbenzoic acid (m-CPBA) in the first step followed by the addition of dibromocarbene (CBr2) to the main monoepoxidation product Pα formed in the first reaction. Calculations were performed using the Becke three-parameter hybrid exchange functional and the Lee–Yang–Parr correlation functional (B3LYP) with the 6-311 + G (d, p) basis set. Transition states were located by QST2, and their highlighting was validated by the existence of only one imaginary frequency in the Hessian matrix. The action of m-CPBA on β-himachalene was analyzed on the two double bonds of β-himachalene whose theoretical calculations show that the attack affects the most substituted double bond on α side containing hydrogen of ring junction. The obtained Pα product thereafter treated with dibromocarbene leads via an exothermic reaction to the six-membered ring double bond position of α-monoepoxide. The major products Pαα are kinetically and thermodynamically favored with a high stereoselectivity in perfect correlation with the experimental observations.http://dx.doi.org/10.1155/2020/8885991 |
| spellingShingle | Sana El Hamidi Malika Khnifira El Mokhtar Lemdek Redouan Hammal Noureddine Barka M’hamed Sadiq Ahmed Benharref Ahmed Chekroun Hssaine Zgou Mohamed Abdennouri Understanding the Mechanism and Selectivities of the Reaction of Meta-Chloroperbenzoic Acid and Dibromocarbene with β-Himachalene: A DFT Study Heteroatom Chemistry |
| title | Understanding the Mechanism and Selectivities of the Reaction of Meta-Chloroperbenzoic Acid and Dibromocarbene with β-Himachalene: A DFT Study |
| title_full | Understanding the Mechanism and Selectivities of the Reaction of Meta-Chloroperbenzoic Acid and Dibromocarbene with β-Himachalene: A DFT Study |
| title_fullStr | Understanding the Mechanism and Selectivities of the Reaction of Meta-Chloroperbenzoic Acid and Dibromocarbene with β-Himachalene: A DFT Study |
| title_full_unstemmed | Understanding the Mechanism and Selectivities of the Reaction of Meta-Chloroperbenzoic Acid and Dibromocarbene with β-Himachalene: A DFT Study |
| title_short | Understanding the Mechanism and Selectivities of the Reaction of Meta-Chloroperbenzoic Acid and Dibromocarbene with β-Himachalene: A DFT Study |
| title_sort | understanding the mechanism and selectivities of the reaction of meta chloroperbenzoic acid and dibromocarbene with β himachalene a dft study |
| url | http://dx.doi.org/10.1155/2020/8885991 |
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