C-C bond formation via C-H bond activation: catalytic arylation and alkenylation of alkane segments.
A new system for catalytic arylation and alkenylation of alkane segments has been developed. The ortho-tert-butylaniline substrates and 2-pivaloylpyridine may be arylated and alkenylated at the tert-butyl group, while no functionalization occurred at more reactive C-H and other bonds. Arylation and alkenylation of these substrates are achieved in the presence of Ph2Si(OH)Me and Ph-CH=CH-Si(OH)Me2, respectively, and the catalytic amount of Pd(OAc)2 and stoichiometric oxidant (Cu(OAc)2, 2 equiv) in DMF. In contrast, the ortho-i-propylaniline substrate underwent cyclopalladation, but no arylation product was obtained. Complex compound 14 was synthesized via tandem arylation-alkenylation of tert-butylaniline 11. We hypothesize that the high selectivity of this system stems from the confluence of directing effect of the Schiff base or pyridine moiety and unique reactivity properties of a phenyl-palladium acetate species (Ph-Pd-OAc.Ln).
Sezen
Bengü
B
Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027, USA.
Franz
Roberto
R
Sames
Dalibor
D
D000473:Alkanes / Q000138:chemical synthesis / Q000737:chemistry*; D000475:Alkenes / Q000138:chemical synthesis*; D002384:Catalysis; D006841:Hydrocarbons, Aromatic / Q000138:chemical synthesis*; D014052:Toluidines / Q000737:chemistry
D000473:Alkanes; D000475:Alkenes; D006841:Hydrocarbons, Aromatic; D014052:Toluidines