Rhodium complexes with planar-chiral cyclopentadienyl ligands: synthesis from tert-butylacetylene and catalytic performance in C-H activation of arylhydroxamates.

The rhodium complex [(C5H2tBu2CH2tBu)RhCl2]2 with an asymmetric cyclopentadienyl ligand was prepared in 95% yield by the reaction of [(cod)RhCl]2 with tert-butylacetylene in the presence of AlCl3. A similar reaction in the presence of InBr3 gave the cationic fulvene complex [(C5H2tBu2 = CHtBu)Rh(cod)]InBr4 (70%), which can add alcohols ROH and produce more bulky catalysts [(C5H2tBu2CH(OR)tBu)RhCl2]2. The enantiomers of these planar-chiral complexes were separated by thin-layer chromatography in the presence of L-phenylglycinol. The complexes catalyze the reactions of arylhydroxamates with alkenes giving dihydroisoquinolones in excellent yields (80-90%), but with moderate enantioselectivity (typically 20-50% ee).