ArticleJournal of the American Chemical Society2017
Chiral Thioureas Promote Enantioselective Pictet-Spengler Cyclization by Stabilizing Every Intermediate and Transition State in the Carboxylic Acid-Catalyzed Reaction.
Article in Journal of the American Chemical Society, 2017. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 27 papers.
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Who cites it
27 citing papers in PubMed, 126 citations in OpenAlex.
- Catalytic enantioselective synthesis of azahelicenes via cascade Pictet-Spengler reaction and dehydrogenative aromatization.Nature communications · 2026Article
- A glycan foldamer that uses carbohydrate-aromatic interactions to perform catalysis.Nature chemistry · 2025Article
- Divergent Enantioselective Total Synthesis of (-)-Ajmalicine, (+)-Mayumbine, and (-)-Roxburghine C.Organic letters · 2025Article
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- Oxoammonium-Catalyzed Ether Oxidation via Hydride Abstraction: Methodology Development and Mechanistic Investigation Using Paramagnetic Relaxation Enhancement NMR.Journal of the American Chemical Society · 2024Article
- Highly Acidic Electron-Rich Brønsted Acids Accelerate Asymmetric Pictet-Spengler Reactions by Virtue of Stabilizing Cation-π Interactions.Journal of the American Chemical Society · 2024Article
- Catalytic enantioselective nitrone cycloadditions enabling collective syntheses of indole alkaloids.Nature communications · 2024Article
- A genetic optimization strategy with generality in asymmetric organocatalysis as a primary target.Chemical science · 2024Article
- Mechanistic Insights into the Stereoselective Cationic Polymerization ofACS catalysis · 2023Article
- Exploring Structure-Function Relationships of Aryl Pyrrolidine-Based Hydrogen-Bond Donors in Asymmetric Catalysis Using Data-Driven Techniques.ACS catalysis · 2022Article
- Dearomatization of Cyclic Diphenylhydrazines: Harnessing theOrganic letters · 2022Article
- Chloride-Mediated Alkene Activation Drives Enantioselective Thiourea and Hydrogen Chloride Co-Catalyzed Prins Cyclizations.Journal of the American Chemical Society · 2022Article
- Catalytic Enantioselective Pictet-Spengler Reaction of α-Ketoamides Catalyzed by a Single H-Bond Donor Organocatalyst.Angewandte Chemie (International ed. in English) · 2022Article
- Biocatalysed synthesis planning using data-driven learning.Nature communications · 2022Article
- Cooperative Hydrogen-Bond-Donor Catalysis with Hydrogen Chloride Enables Highly Enantioselective Prins Cyclization Reactions.Journal of the American Chemical Society · 2021Article
- Enantioselective, Catalytic Multicomponent Synthesis of Homoallylic Amines Enabled by Hydrogen-Bonding and Dispersive Interactions.Journal of the American Chemical Society · 2021Article
- Synthesis of aza-quaternary centersChemical science · 2021Article
- Asymmetric Nazarov Cyclizations of Unactivated Dienones by Hydrogen-Bond-Donor/Lewis Acid Co-Catalyzed, Enantioselective Proton-Transfer.Advanced synthesis & catalysis · 2020Article
- Mechanism and origins of selectivity in the enantioselective oxa-Pictet-Spengler reaction: a cooperative catalytic complex from a hydrogen bond donor and chiral phosphoric acid.Chemical science · 2020Article
- A Selenourea-Thiourea Brønsted Acid Catalyst Facilitates Asymmetric Conjugate Additions of Amines to α,β-Unsaturated Esters.Journal of the American Chemical Society · 2020Article
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4 authors at 1 institution in 1 country.
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Abstract
An investigation of the mechanism of benzoic acid/thiourea co-catalysis in the asymmetric Pictet-Spengler reaction is reported. Kinetic, computational, and structure-activity relationship studies provide evidence that rearomatization via deprotonation of the pentahydro-β-carbolinium ion intermediate by a chiral thiourea·carboxylate complex is both rate- and enantioselectivity-determining. The thiourea catalyst induces rate acceleration over the background reaction mediated by benzoic acid alone by stabilizing every intermediate and transition state leading up to and including the final selectivity-determining step. Distortion-interaction analyses of the transition structures for deprotonation predicted using density functional theory indicate that differential π-π and C-H···π interactions within a scaffold organized by multiple hydrogen bonds dictate stereoselectivity. The principles underlying rate acceleration and enantiocontrol described herein are expected to have general implications for the design of selective transformations involving deprotonation of high-energy intermediates.
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