Regioselective unsymmetrical tetraallylation of C(60) through palladium catalysis.
A Pd-catalyzed tetraallylation of C(60) that selectively occurs with an unsymmetrical addition pattern has been established. Treatment of C(60) with CH(2)=CHCH(2)Cl, CH(2)=CHCH(2)SnBu(3), and PdCl(2)[P(OPh)(3)](2) in 1,2-Cl(2)C(6)H(4) at 50 degrees C afforded the tetraallylated fullerene in 74% yield with virtually complete regioselectivity. Mechanistic investigations showed that (i) tetraallylation proceeds through consecutive nucleophilic/electrophilic allylations [likely via a bis(pi-allyl)palladium intermediate] and (ii) both steric (for the first diallylation) and electronic (for the second diallylation) factors are responsible for the high regioselectivity.
Nambo
Masakazu
M
Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan.
Wakamiya
Atsushi
A
Yamaguchi
Shigehiro
S
Itami
Kenichiro
K
D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D037741:Fullerenes / Q000737:chemistry*; D007536:Isomerism; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*
D000498:Allyl Compounds; D037741:Fullerenes; D010165:Palladium; C069837:fullerene C60