Diastereo- and enantioselective dearomatization of rhenium-bound naphthalenes.

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.

Strategy for the resolution of a chiral dearomatization agent:[TpRe(CO)(1-methylimidazole)] coordination of alpha-pinene (Tp = hydridotris(pyrazolyl)borate).

A methodology for resolving TpRe(CO)(1-methylimidazole)(eta(2)-benzene) has been developed utilizing (R)-alpha-pinene. Each enantiomer of the [TpRe(CO)(MeIm)] system can be obtained with the enantiomer ratio (er) = 97:3 by taking advantage of differing rates of pinene substitution for the two diastereomers of TpRe(CO)(MeIm)(eta(2)-(R)-alpha-pinene).

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.