The Rappe Rearrangement. The origin of cis-stereoselectivity in the conversion of 2,3-dibromo-2-methyl-cyclopropan-1-one to (Z)-but-2-enoic acid. TS3 and TS4 pathways
DOI: 10.14469/hpc/11044 Metadata
Created: 2022-08-26 06:52
Last modified: 2025-05-14 09:05
License: Creative Commons: Public Domain Dedication 1.0
Funding: (none given)
Description
Gaussian 16 calculations
Member of collection / collaboration
| DOI | Description |
|---|---|
| 10.14469/hpc/11172 | The Mechanism of the Rappe Rearrangement – a stereochemical investigation using Density Functional Theory. |
Members
| DOI | Description |
|---|---|
| 10.14469/hpc/11050 | Rappe Rearrangement. Bicyclooxirane formation, cis, final opening retro 2+2, GS for TS4, Def2-TZVPP, G = -2880.747773 |
| 10.14469/hpc/11048 | Rappe Rearrangement. Bicyclooxirane formation, trans, final opening, GS for TS4, retro 2+2, Def2-TZVPP, G = 2880.751741, TS4, G = -2880.728398, DG = 14.7 |
| 10.14469/hpc/11199 | Rappe Rearrangement. BicycloOxirane formation, Sn2, cis, TS3, Na+.4H2O, Def2-TZVPP, G = -3348.724114, DG = 36.4 |
| 10.14469/hpc/11054 | Rappe Rearrangement. TS3, trans, Def2-TZVPP, -2880.720560, ΔG = 19.6 |
| 10.14469/hpc/10894 | Rappe Rearrangement. Bicyclooxirane formation, final opening retro 2+2, TS4, OH...Br H bond, trans, Def2-SVPP, G = -2880.032364 |
| 10.14469/hpc/11049 | Rappe Rearrangement. TS3, G = -2880.715927, ΔG = 24.5 |
| 10.14469/hpc/11179 | Rappe Rearrangement. Bicyclooxirane, intermediate between TS3 and TS4, Def2-TZVPP, G = -2880.746675, 3.2 kcal higher than reactant. |
| 10.14469/hpc/11047 | Rappe Rearrangement. TS4, G = -2880.722473, ΔG = 18.4 |
| 10.14469/hpc/10873 | Rappe Rearrangement. Bicyclooxirane formation, Sn2, cis, TS3, Def2-SVPP, G = -2880.015999, DG = 23.9 |
| 10.14469/hpc/10876 | Rappe Rearrangement. Bicyclooxirane formation, Sn2, TS3, trans, Def2-SVPP, G = -2880.019977 |
| 10.14469/hpc/10889 | Rappe Rearrangement. Bicyclooxirane formation, Sn2, TS3, trans, Def2-SVPP, G = -2880.019977, DDG = 2.5, IRC |
| 10.14469/hpc/11183 | Rappe Rearrangement. Bicyclooxirane formation, cis, final opening retro 2+2, TS4, Def2-SVPP, OH...Br H bond G = -2880.026702, IRC, reverse phase (H-bond discontinuity) |
| 10.14469/hpc/11192 | Rappe Rearrangement. BicycloOxirane formation, Sn2, cis, TS3, 4H2O.Na, Def2-SVPP, G = -3347.522021, IRC |
| 10.14469/hpc/11228 | Rappe Rearrangement. FAIR Data Table 3. Free energies for Cyclisation of dibromoenols. TS3/TS4 |
| 10.14469/hpc/10890 | Rappe Rearrangement. Bicyclooxirane formation, Sn2, cis, TS3, Def2-SVPP, -2880.015999 IRC |
| 10.14469/hpc/11189 | Rappe Rearrangement. Bicyclo-oxirane formation with Sn2, cis, GS for TS2/3, Def2-SVPP, (-2880.015999) G = -2880.054068 |
| 10.14469/hpc/11187 | Rappe Rearrangement. BicycloOxirane formation, Sn2, cis, TS3, 4H2O.Na, Def2-SVPP, G = -3347.522021, DG = 37.1 |
| 10.14469/hpc/10904 | Rappe Rearrangement. Bicyclooxirane formation, trans, final opening retro 2+2, TS4, Def2-SVPP, OH...Br H bond, G = -2880.032364 IRC |
| 10.14469/hpc/10886 | Rappe Rearrangement. Bicyclooxirane formation, cis, final opening retro 2+2, TS4, Def2-SVPP, OH...Br H bond G = -2880.026702 |
Associated DOIs
| Current dataset ... | DOI | Description |
|---|---|---|
| References | 10.14469/hpc/11175 | The Rappe Rearrangement. Ring opening, (trans), Def2-TZVPP, GS for TS2/3, G = -2880.751741 |
| References | 10.14469/hpc/11188 | The Rappe Rearrangement. BicycloOxirane formation, Sn2, cis, GS for TS2/3, 4H2O.Na, Def2-SVPP, G = -3347.581100 |