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Mechanism-Guided Development of a Highly Active Bis-thiourea Catalyst for Anion-Abstraction Catalysis.

ABSTRACT: We describe the rational design of a linked, bis-thiourea catalyst with enhanced activity relative to monomeric analogues in a representative enantioselective anion-abstraction reaction. Mechanistic insights guide development of this linking strategy to favor substrate activation though the intramolecular cooperation of two thiourea subunits while avoiding nonproductive aggregation. The resulting catalyst platform overcomes many of the practical limitations that have plagued hydrogen-bond-donor catalysis and enables use of catalyst loadings as low as 0.05 mol %. Computational analyses of possible anion-binding modes provide detailed insight into the precise mechanism of anion-abstraction catalysis with this pseudo-dimeric thiourea.

SUBMITTER: Kennedy CR

PROVIDER: S-EPMC5380606 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature

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Mechanism-Guided Development of a Highly Active Bis-thiourea Catalyst for Anion-Abstraction Catalysis.

Kennedy C Rose CR Lehnherr Dan D Rajapaksa Naomi S NS Ford David D DD Park Yongho Y Jacobsen Eric N EN

Journal of the American Chemical Society 20161011 41

We describe the rational design of a linked, bis-thiourea catalyst with enhanced activity relative to monomeric analogues in a representative enantioselective anion-abstraction reaction. Mechanistic insights guide development of this linking strategy to favor substrate activation though the intramolecular cooperation of two thiourea subunits while avoiding nonproductive aggregation. The resulting catalyst platform overcomes many of the practical limitations that have plagued hydrogen-bond-donor ...[more]

PMID: 27704810

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