Carbon–hydrogen and C–X (X = Cl or SiMe3) bond activation. 1-Cyclopalladation and oxidation of some derivatives of 2-[(dimethylamino)methyl]naphthalene

摘要: The regioselective palladation reactions of 3-substituted derivatives 2-[(dimethylamino)methyl]naphthalene, C10H6(CH2NMe2)-2-R-3 (R = Cl, SiMe3 or OSiMe3), were studied. For the substrate with R no cyclopalladation at position 1 was observed and co-ordination complex isolated. 3-palladated product formed in 10% yield via C–Cl activation. reaction 2-[(dimethylamino)methyl]-3-methylnaphthalene Pd(O2CMe)2 work-up LiCl did lead to 1, resulting being isolated 96% yield. crystal structure bis(acetonitrile){2-[(dimethylamino)methyl]-3-methyl-1-naphthyl}palladium trifluoromethanesulfonate solved. Monoclinic, space group P21/n, a= 13.193(1), b= 11.801(1), c= 14.797(1)A, β= 105.15(1)°, Z= 4. refined R= 0.042 for 3455 reflections I > 2.5σ(I). Palladation also achieved by oxidative addition 1-bromo-2-[(dimethylamino)methyl]naphthalene [Pd(dba)2](dba dibenzylideneacetone). Protection C(3) resulted quantitative replacement palladium. Silicon–oxygen bond cleavage when OSiMe3 treated Pd(O2CMe)2. Palladium bis{3-[(dimethylamino)methyl]-2-naphtholate} obtained quantitatively. Oxidation several arylpalladium complexes ButO2H presence [VO(acac)2](acac acetylacetonate) [{RhCl(cod)}2]}(cod cycloocta-1,5-diene) as catalyst. corresponding 1-naphthols prepared yields varying from 33 78%. In a number cases 1,4-naphthoquinones 18 38%.