The Willgerodt-Kindler Reaction: mechanistic reality check 1.
DOI: 10.14469/hpc/7294 Metadata
Created: 2020-07-20 20:11
Last modified: 2020-09-06 16:44
License: Creative Commons: Public Domain Dedication 1.0
Funding: (none given)
Description
The Willgerodt reaction[cite]10.1002/cber.18870200278[/cite], discovered in 1887 and shown below, represents a transformation with a once famously obscure mechanism. A major step in the elucidation of that mechanism came[cite]10.1021/ja01157a034[/cite] using the then new technique of 14C radio-labelling, shortly after the atom bomb projects during WWII made 14CO2 readily available to researchers. Here I am going to start the process of applying the far more recent technique of quantitative quantum mechanical modelling to see if some of the proposed mechanisms stand up to its scrutiny
Member of collection / collaboration
| DOI | Description |
|---|---|
| 10.14469/hpc/7385 | The Willgerodt-Kindler reaction. Completing the Box set. |
Members
| DOI | Description |
|---|---|
| 10.14469/hpc/7279 | Willgerodt TS1 G = -994.444940 DG3BJ G = -994.508737 DG = 27.9 |
| 10.14469/hpc/7282 | Willgerodt Product G = -994.586897 DG = -21.2 |
| 10.14469/hpc/7278 | Willgerodt-Kindler reactant (zwitterion) G = -994.487744 DG3BJ G = -994.553137 |
| 10.14469/hpc/7283 | Willgerodt Thiirane G = -994.553747 Int3 DG = -0.4 |
| 10.14469/hpc/7277 | Willgerodt TS2 G = -994.460005 Ph rotamer DG3BJ G = -994.526229 |
| 10.14469/hpc/7275 | Willgerodt Int2 G = -994.459625 Rotamer DG3BJ G = -994.529692 |
| 10.14469/hpc/7287 | Willgerodt-Kindler reactant (protonated) DG3BJ G = -995.002362 DG = 0.0 |
| 10.14469/hpc/7301 | Willgerodt TS3 (final 1,2-H shift) DG3BJ G = -994.485324 DG = 42.6 IRC reverse |
| 10.14469/hpc/7293 | Willgerodt TS1 (protonated) G = -994.931648 DG = 44.4 |
| 10.14469/hpc/7292 | Willgerodt Int1 (protonated) DG3BJ G = -994.981709 DG = 13.0 |
| 10.14469/hpc/7302 | Willgerodt TS3 (final 1,2-H shift) DG3BJ G = -994.485324 DG = 42.6 IRC forward |
| 10.14469/hpc/7288 | Willgerodt Int2 (protonated) G = -994.966716 DG = 22.4 |
| 10.14469/hpc/7276 | Willgerodt Int1 G = -994.478929 Rotamer GD3BJ G = -994.543835 |
| 10.14469/hpc/7286 | Willgerodt Int3 DG3BJ G = -994.488524 DG = 40.5 |
| 10.14469/hpc/7285 | Willgerodt TS3 (final 1,2-H shift) DG3BJ G = -994.485324 DG = 42.6 |
Associated DOIs
| Current dataset ... | DOI | Description |
|---|---|---|
| References | 10.14469/hpc/7336 | The Willgerodt-Kindler Reaction: mechanistic reality check 1. |
| References | 10.14469/hpc/7356 | The Willgerodt-Kindler Reaction: mechanistic reality check 3. |