ja311208a_si_002.pdf (2.13 MB)
Chiral-Anion-Dependent Inversion of Diastereo- and Enantioselectivity in Carbonyl Crotylation via Ruthenium-Catalyzed Butadiene Hydrohydroxyalkylation
journal contribution
posted on 2012-12-26, 00:00 authored by Emma L. McInturff, Eiji Yamaguchi, Michael J. KrischeThe ruthenium catalyst generated in situ from H2Ru(CO)(PPh3)3, (S)-SEGPHOS,
and a TADDOL-derived
phosphoric acid promotes butadiene hydrohydroxyalkylation to form
enantiomerically enriched products. Notably, the observed diastereo-
and enantioselectivity is the opposite of that observed using BINOL-derived
phosphate counterions in combination with (S)-SEGPHOS,
the same enantiomer of the chiral ligand. Match/mismatch effects between
the chiral ligand and the chiral TADDOL-phosphate counterion are described.
For the first time, single-crystal X-ray diffraction data for a ruthenium
complex modified by a chiral phosphate counterion are reported.