Ligand-modulated stereo- and regioselective tandem addition reactions of rhenium-bound naphthalene.
A series of complexes of the form TpRe(CO)(L)(eta(2)-naphthalene) (Tp = hydridotris(pyrazolyl)borate) undergoes tandem electrophile/nucleophile addition reactions with a high degree of regiocontrol depending on the auxiliary ligand, L. When L = PMe(3), the reaction of the eta(2)-naphthalene complex with triflic acid followed by a silyl ketene acetal favors the 1,4-addition product, whereas when L = pyridine, N,N-dimethylaminopyridine, N-methylimidazole, or NH(3) the 1,2-addition product is favored. These reactions proceed with excellent stereocontrol: both electrophile (H(+), D(+)) and nucleophile (silyl ketene acetal) add anti to the face of metal coordination, and a single coordination diastereomer can be isolated for each reaction. One-electron oxidation of the Re complex affords the corresponding free dihydronaphthalene in good yield.
Valahovic
Mark T
MT
Department of Chemistry, University of Virginia, Charlottesville, VA 22901, USA.
Gunnoe
T Brent
TB
Sabat
Michal
M
Harman
W Dean
WD
D018360:Crystallography, X-Ray; D015394:Molecular Structure; D009281:Naphthalenes / Q000138:chemical synthesis / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*; D013237:Stereoisomerism
D009281:Naphthalenes; D009942:Organometallic Compounds; D012211:Rhenium