Diastereo- and enantioselective dearomatization of rhenium-bound naphthalenes |
| |
Authors: | Ding Fei Valahovic Mark T Keane Joseph M Anstey Mitchell R Sabat Michal Trindle Carl O Harman W Dean |
| |
Institution: | Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904-4319, USA. |
| |
Abstract: | Dihapto-coordinated naphthalene complexes of the form TpRe(CO)(L)(eta(2)-naphthalene) (L = PMe(3), pyridine, or 1-methylimidazole) undergo electrophilic addition with dimethoxymethane and with various Michael acceptors to generate 1H-naphthalenium species. These naphthalenium complexes undergo intra- or intermolecular nucleophilic addition reactions with stabilized enolates, silyl ketene acetals, or enols to form the corresponding dihydronaphthalene complexes. Oxidative decomplexation generates the free dihydronaphthalene. When a resolved form of the rhenium dearomatization agent is used, these reactions can be performed enantioselectively. DFT calculations provide a useful guide in explaining the observed stereochemistry. Depending on reaction conditions, a Michael-Michael ring-closure sequence (MIMIRC) or a net 2 + 4] cycloaddition with the bound naphthalene is also observed, and the corresponding tricyclic molecules can be removed from the metal in high yield. |
| |
Keywords: | |
本文献已被 PubMed 等数据库收录! |
|