Construction of Enantioenriched [3.1.0] Bicycles via a Ruthenium-Catalyzed Asymmetric Redox Bicycloisomerization Reaction
- 24 November 2014
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 136 (50), 17422-17425
- https://doi.org/10.1021/ja510968h
Abstract
Enantiomerically enriched [3.1.0] bicycles containing vicinal quaternary centers were synthesized from [1,6]-enynes using a cyclopentadienylruthenium catalyst containing a tethered chiral sulfoxide. The reaction was complicated by the fact that the substrates contained a racemic propargyl alcohol that could affect the selectivity of the process. Nonetheless, high levels of enantioinduction were observed, despite complications arising from the use of racemic substrates. Mechanistic studies showed that while the utilization of either enantiomer of the propargyl alcohol led to high product enantiomeric ratios when the reaction was conducted in acetone, a significant matched/mismatched effect was observed in tetrahydrofuran.Funding Information
- Division of Chemistry (CHE-1145236)
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