Journal
ACS CENTRAL SCIENCE
Volume 2, Issue 6, Pages 416-423Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscentsci.6b00125
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Funding
- NIGMS NIH HHS [R01 GM043214, R37 GM043214] Funding Source: Medline
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Sigmatropic rearrangements number among the most powerful complexity-building transformations in organic synthesis but have remained largely insensitive to enantioselective catalysis due to the diffuse nature of their transition structures. Here, we describe a synergistic ion-binding strategy for asymmetric catalysis of anionic sigmatropic rearrangements. This approach is demonstrated with the enantioselective [2,3]-Wittig rearrangement of a-allyloxy carbonyl compounds to afford highly enantioenriched homoallylic alcohol products. Chiral thiourea catalysts are shown to engage reactive anions and their countercations through a cooperative set of attractive, noncovalent interactions. Catalyst structure-reactivity-selectivity relationship studies and computational analyses provide insight into catalyst-substrate interactions responsible for enantioinduction and allude to the potential generality of this catalytic strategy.
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