Chiral organochlorosilanes derived from terpenes: diastereoselective hydrosilylation of methylene bicyclo[2.2.1]heptanes with HSiMenCln-2 (n=0-2)

The H₂PtCl₆ catalysed hydrosilylation of the terpenes (+)-α-fenchene (XI), (−)-2-methylene bornane (XII), (+)-camphene (XIII) and (−)-3-methylene fenchane (XIV) using HSiMe₂Cl or HSiMeCl₂ proceeds with high regioselectively and in some cases, with high diastereoselectivity. KF-assisted oxidation of the hydrosilylation products gives predominately endo-terpene alcohols. The alcohols have inverted endo/exo ratios to those formed by oxidative hydroboration. Reaction of XIV with HSiMe₂Cl or HSiMeCl₂ is accompanied by a clean rearrangement of the isocamphane skeleton into (+)-2-methylene bornane (XII) prior to hydrosilylation.

The hydrosilylation of α-fenchene, 2-methylene bornane, camphene and 3-methylene fenchane with chlorosilanes HSiMe_nCl_n − 2 (n=0–2) occurred with varying degrees of diastereoselectivity providing anti-Markovnikov product mixtures, in which the endo-isomers dominate over the exo-isomers. These mixtures were oxidized to give the corresponding terpene alcohols. 3-Methylene fenchane undergoes a rearrangement into 2-methylene bornane prior to hydrosilylation.