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. 2012 Dec 26;134(51):20628-31.
doi: 10.1021/ja311208a. Epub 2012 Dec 12.

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

Emma L McInturff  1 , Eiji Yamaguchi, Michael J Krische
Affiliations

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

Emma L McInturff et al. J Am Chem Soc. .

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.

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Figures

Figure 1
Figure 1
Ruthenium catalyzed diastereo- and enantioselective crotylation via butadiene hydrohydroxyalkylation.
Figure 2
Figure 2
Structure of Ru(CO)(OAc)(A2-phosphate)[(S)-SEGPHOS)] as determined by single crystal X-ray diffraction analysis. Displacement ellipsoids are scaled to the 50% probability level.
Scheme 1
Scheme 1
Chiral phosphate counterion dependent inversion of diastereo- and enantioselectivity using the chiral catalyst modified by (S)-SEGPHOS. aReaction performed at 105 °C.
Scheme 2
Scheme 2
Catalytic mechanism for ruthenium catalyzed crotylation via butadiene hydrohydroxyalkylation.
See this image and copyright information in PMC

References

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