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Lithium Diisopropylamide-Mediated Enolizations: Solvent-Independent Rates, Solvent-Dependent Mechanisms
| Content Provider | Semantic Scholar |
|---|---|
| Author | Sun, Xiufeng Collum, David B. |
| Copyright Year | 2000 |
| Abstract | Rate studies of a lithium diisopropylamide-mediated ester enolization reveal solvation effects that are not in accord with expectation. Metalations in THF, t-BuOMe, HMPA/THF, and DMPU/THF (HMPA = hexamethylphosphoramide, DMPU = 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone) occur at nearly the same rates, yet proceed via four fundamentally distinct scenarios: (1) disolvated monomer in THF, (2) monosolvated dimer in t-BuOMe, (3) both monosolvated monomer and tetrasolvated dimer in HMPA/THF, and (4) mono- and disolvated monomers in DMPU/THF. The implication of reactive open dimers in t-BuOMe and triple ions in HMPA/THF underscores the importance of aggregate-based reactions. |
| Starting Page | 2452 |
| Ending Page | 2458 |
| Page Count | 7 |
| File Format | PDF HTM / HTML |
| DOI | 10.1021/ja992062z |
| Volume Number | 122 |
| Alternate Webpage(s) | http://collum.chem.cornell.edu/publications/69.pdf |
| Alternate Webpage(s) | https://doi.org/10.1021/ja992062z |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
