Steps toward Rationalization of the Enantiomeric Excess of the Sakurai–Hosomi–Denmark Allylation Catalyzed by Biisoquinoline N,N’-Dioxides Using Computations
Allylation reactions of aldehydes are chemical transformations of fundamental interest, as they give direct access to chiral homoallylic alcohols. In this work, we focus on the full computational characterization of the catalytic activity of substituted biisoquinoline-N,N’-dioxides for the allylatio...
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MDPI AG
2021-12-01
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| Series: | Catalysts |
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| Online Access: | https://www.mdpi.com/2073-4344/11/12/1487 |
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| author | Pierpaolo Morgante Coty Deluca Tegla E. Jones Gregory J. Aldrich Norito Takenaka Roberto Peverati |
| author_facet | Pierpaolo Morgante Coty Deluca Tegla E. Jones Gregory J. Aldrich Norito Takenaka Roberto Peverati |
| author_sort | Pierpaolo Morgante |
| collection | DOAJ |
| description | Allylation reactions of aldehydes are chemical transformations of fundamental interest, as they give direct access to chiral homoallylic alcohols. In this work, we focus on the full computational characterization of the catalytic activity of substituted biisoquinoline-N,N’-dioxides for the allylation of 2-naphthaldehyde. We characterized the structure of all transition states as well as identified the π stacking interactions that are responsible for their relative energies. Motivated by disagreement with the experimental results, we also performed an assessment of 34 different density functional methods, with the goal of assessing DFT as a general tool for understanding this chemistry. We found that the DFT results are generally consistent as long as functionals that correctly account for dispersion interactions are used. However, agreement with the experimental results is not always guaranteed. We suggest the need for a careful synergy between computations and experiments to correctly interpret the data and use them as a design tool for new and improved asymmetric catalysts. |
| first_indexed | 2024-03-10T04:27:03Z |
| format | Article |
| id | doaj.art-b349ed038a2d4b0f9f17540e454c5cb8 |
| institution | Directory Open Access Journal |
| issn | 2073-4344 |
| language | English |
| last_indexed | 2024-03-10T04:27:03Z |
| publishDate | 2021-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Catalysts |
| spelling | doaj.art-b349ed038a2d4b0f9f17540e454c5cb82023-11-23T07:34:21ZengMDPI AGCatalysts2073-43442021-12-011112148710.3390/catal11121487Steps toward Rationalization of the Enantiomeric Excess of the Sakurai–Hosomi–Denmark Allylation Catalyzed by Biisoquinoline N,N’-Dioxides Using ComputationsPierpaolo Morgante0Coty Deluca1Tegla E. Jones2Gregory J. Aldrich3Norito Takenaka4Roberto Peverati5Chemistry Program, Florida Institute of Technology, 150 W. University Blvd., Melbourne, FL 32901, USAChemistry Program, Florida Institute of Technology, 150 W. University Blvd., Melbourne, FL 32901, USAChemistry Program, Florida Institute of Technology, 150 W. University Blvd., Melbourne, FL 32901, USAChemistry Program, Florida Institute of Technology, 150 W. University Blvd., Melbourne, FL 32901, USAChemistry Program, Florida Institute of Technology, 150 W. University Blvd., Melbourne, FL 32901, USAChemistry Program, Florida Institute of Technology, 150 W. University Blvd., Melbourne, FL 32901, USAAllylation reactions of aldehydes are chemical transformations of fundamental interest, as they give direct access to chiral homoallylic alcohols. In this work, we focus on the full computational characterization of the catalytic activity of substituted biisoquinoline-N,N’-dioxides for the allylation of 2-naphthaldehyde. We characterized the structure of all transition states as well as identified the π stacking interactions that are responsible for their relative energies. Motivated by disagreement with the experimental results, we also performed an assessment of 34 different density functional methods, with the goal of assessing DFT as a general tool for understanding this chemistry. We found that the DFT results are generally consistent as long as functionals that correctly account for dispersion interactions are used. However, agreement with the experimental results is not always guaranteed. We suggest the need for a careful synergy between computations and experiments to correctly interpret the data and use them as a design tool for new and improved asymmetric catalysts.https://www.mdpi.com/2073-4344/11/12/1487DFTLewis basesorganocatalysisallyltrichlorosilane |
| spellingShingle | Pierpaolo Morgante Coty Deluca Tegla E. Jones Gregory J. Aldrich Norito Takenaka Roberto Peverati Steps toward Rationalization of the Enantiomeric Excess of the Sakurai–Hosomi–Denmark Allylation Catalyzed by Biisoquinoline N,N’-Dioxides Using Computations Catalysts DFT Lewis bases organocatalysis allyltrichlorosilane |
| title | Steps toward Rationalization of the Enantiomeric Excess of the Sakurai–Hosomi–Denmark Allylation Catalyzed by Biisoquinoline N,N’-Dioxides Using Computations |
| title_full | Steps toward Rationalization of the Enantiomeric Excess of the Sakurai–Hosomi–Denmark Allylation Catalyzed by Biisoquinoline N,N’-Dioxides Using Computations |
| title_fullStr | Steps toward Rationalization of the Enantiomeric Excess of the Sakurai–Hosomi–Denmark Allylation Catalyzed by Biisoquinoline N,N’-Dioxides Using Computations |
| title_full_unstemmed | Steps toward Rationalization of the Enantiomeric Excess of the Sakurai–Hosomi–Denmark Allylation Catalyzed by Biisoquinoline N,N’-Dioxides Using Computations |
| title_short | Steps toward Rationalization of the Enantiomeric Excess of the Sakurai–Hosomi–Denmark Allylation Catalyzed by Biisoquinoline N,N’-Dioxides Using Computations |
| title_sort | steps toward rationalization of the enantiomeric excess of the sakurai hosomi denmark allylation catalyzed by biisoquinoline n n dioxides using computations |
| topic | DFT Lewis bases organocatalysis allyltrichlorosilane |
| url | https://www.mdpi.com/2073-4344/11/12/1487 |
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