| FAIR Data table.a Computed relative reaction free energies (kcal/nol-1) of Obtusallene derived oxonium and chloronium cations | ||||
|---|---|---|---|---|
| Epoxide ring opening/oxonium cation formation | ||||
| Ring opening the epoxide | Reactant: 0.0 , bj96b Product: -17.5 , bj83 | TS C13: 1.5 , bjmx | TS C12: 0.9 , bkr9 | |
| Oxonium ion pair | ||||
| C-O NBO | C6-O | C9-O | C12-O, bnc8 | |
| Nucleophilic attack on oxonium cation | ||||
| Nucleophile | C6 | C9 | C12 | |
| MeOH | 21.9c bfd2 | 23.2 , bjqc 32.1d bfcs | 21.3, bfcr 0.0 , bj96 (reactant), 2.0 , bj99 (product) | |
| 2MeOH | - | 26.4 , bjnj | 18.8 , bjmw 0.0 , bnhz (reactant) | |
| Br(-) | 18.0 (16.1D) bfcj | 17.5 (14.5D), bfck | 14.7 (11.1D), bfcm 0.0, bnrd (reactant) | |
| MeO(-) | 21.1 (15.5D), bfcn | 18.6 (15.5D), bfcp | 10.9 (11.0D), bfcq 0.0 , bnh6 (Reactant) | |
| Nucleophilic attack on chloronium cation | ||||
| MeOH | 14.7 , bj8z | 15.8 , bj95 | 16.2 , bj82 0.0 , bnc7 (reactant) | |
| Nucleophilic attack on oxonium cation/BF4 anion ion-pair | ||||
| MeOH | 20.0 (24.5D), bksg | 20.3 (15.0D), bj97 | 20.5 , bj98 0.0 , bnhq (reactant) | |
| aClick on any energy to load a 3D-coordinate for a ωB97XD/Def2-TZVPPD/SCRF=methanol model. bRDM (Research data management) DOI, resolved as e.g. http://doi.org/bj96 cΔG‡298 for transition state, kcal mol-1 dAlternative conformation for 8-ring. | ||||