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Chiral-anion-dependent inversion of diastereo- and enantioselectivity in carbonyl crotylation via ruthenium-catalyzed butadiene hydrohydroxyalkylation.

ABSTRACT: The ruthenium catalyst generated in situ from H(2)Ru(CO)(PPh(3))(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.

SUBMITTER: McInturff EL

PROVIDER: S-EPMC3531795 | biostudies-literature | 2012 Dec

REPOSITORIES: biostudies-literature

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Chiral-anion-dependent inversion of diastereo- and enantioselectivity in carbonyl crotylation via ruthenium-catalyzed butadiene hydrohydroxyalkylation.

McInturff Emma L EL Yamaguchi Eiji E Krische Michael J MJ

Journal of the American Chemical Society 20121212 51

The ruthenium catalyst generated in situ from H(2)Ru(CO)(PPh(3))(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 counteri ...[more]

PMID: 23234459

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