Epoxidation of alkenes by peracids: A refined view of textbook mechanisms based on a quantum mechanically derived curly-arrow depiction
DOI: 10.14469/hpc/3603 Metadata
Created: 2018-02-09 17:05
Last modified: 2019-08-10 17:45
License: Creative Commons: Public Domain Dedication 1.0
Funding: (none given)
Co-author: Gerald Knizia Co-author: Johannes E. M. N. Klein
Description
Using the intrinsic bond orbital (IBO) analysis based on accurate quantum mechanical calculations of the reaction path for the epoxidation of propene using peroxyacetic acid, we find that the four commonly used curly arrows for representing this reaction mechanism are insufficient and that seven curly arrows are required as a result of changes to σ and π bonding interactions, which are usually neglected in all textbook curly arrow representations. The IBO method provides a convenient quantitative method for deriving curly arrows in a rational manner rather than the normal ad hoc representations used ubiquitously in teaching organic chemistry.
Files
| Filename | Size | Type | Description |
|---|---|---|---|
| ESI-2019-05-07.docx | 281KB | application/vnd.openxmlformats-officedocument.wordprocessingml.document | Supporting information |
Members
| DOI | Description |
|---|---|
| 10.14469/hpc/4783 | Peracetic acid epoxidation of trans-dicyanopropene. |
| 10.14469/hpc/3631 | Peracetic acid expoxidation of nitroethene |
| 10.14469/hpc/3629 | Peracetic acid expoxidation of cis-dicyanoethene |
| 10.14469/hpc/4812 | Epoxidation of Alkenes by Peracids: Calculated kinetic isotope effects |
| 10.14469/hpc/4814 | Peracetic acid epoxidation of aminoethene |
| 10.14469/hpc/4966 | Epoxidation of Alkenes by Peracids: Molden file archives |
| 10.14469/hpc/4931 | FAIR Data table. Epoxidation of alkenes by peracids: A refined view of textbook mechanisms based on a quantum mechanically derived curly-arrow depiction |
| 10.14469/hpc/4785 | Peracetic acid epoxidation of cis-dicyanopropene. |
| 10.14469/hpc/3628 | Peracetic acid expoxidation of cyanoethene |
| 10.14469/hpc/3632 | Peracetic acid expoxidation of hydroxyethene |
| 10.14469/hpc/3627 | Peracetic acid expoxidation of propene |
| 10.14469/hpc/3630 | Peracetic acid expoxidation of trans-dicyanoethene |
Associated DOIs
| Current dataset ... | DOI | Description |
|---|---|---|
| References | 10.1002/anie.201410637 | Published article: Electron Flow in Reaction Mechanisms—Revealed from First Principles |
| References | 10.1002/open.201900099 | Published article: Epoxidation of Alkenes by Peracids: From Textbook Mechanisms to a Quantum Mechanically Derived Curly-Arrow Depiction |
| References | 10.1002/open.201900099 | Published article: Epoxidation of Alkenes by Peracids: From Textbook Mechanisms to a Quantum Mechanically Derived Curly-Arrow Depiction |
| References | 10.1021/ct400687b | Published article: Intrinsic Atomic Orbitals: An Unbiased Bridge between Quantum Theory and Chemical Concepts |
| References | 10.14469/hpc/4041 | Viewing and re-using Computational, Spectroscopic and Crystallographic FAIR Data |