ArticleJournal of the American Chemical Society2020
Mechanistic Studies Inform Design of Improved Ti(salen) Catalysts for Enantioselective [3 + 2] Cycloaddition.
Article in Journal of the American Chemical Society, 2020. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 16 papers.
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Who cites it
16 citing papers in PubMed.
- Titanium-Mediated Organic Electrosynthesis.ACS catalysis · 2025Review
- Identification of Ti(salen) Complexes for Efficient Catalysis in Single-Electron Steps by Cyclic Voltammetry.Angewandte Chemie (International ed. in English) · 2025Article
- Titanium catalyzed [2σ + 2π] cycloaddition of bicyclo[1.1.0]-butanes with 1,3-dienes for efficient synthesis of stilbene bioisosteres.Nature communications · 2024Article
- Metalloradical Catalysis: General Approach for Controlling Reactivity and Selectivity of Homolytic Radical Reactions.Angewandte Chemie (International ed. in English) · 2024Review
- Alkyl Cyclopropyl Ketones in Catalytic Formal [3 + 2] Cycloadditions: The Role of SmIJournal of the American Chemical Society · 2024Article
- Ligand-Metal Cooperation Enables Net Ring-Opening C-C Activation / Difunctionalization of Cyclopropyl Ketones.ACS catalysis · 2023Article
- Enantioselective radical cascade cyclization via Ti-catalyzed redox relay.Tetrahedron letters · 2023Article
- Formal Cycloadditions Driven by the Homolytic Opening of Strained, Saturated Ring Systems.Angewandte Chemie (International ed. in English) · 2023Review
- Paired electrolysis-enabled nickel-catalyzed enantioselective reductive cross-coupling between α-chloroesters and aryl bromides.Nature communications · 2022Article
- Article
- Diastereoselective and enantioselective photoredox pinacol coupling promoted by titanium complexes with a red-absorbing organic dye.Chemical science · 2022Article
- Identifying the true origins of selectivity in chiral phosphoric acid catalyzedChemical science · 2021Article
- Enantioselective palladaelectro-catalyzed C-H olefinations and allylations for N-C axial chirality.Chemical science · 2021Article
- Origin of enantioselectivity reversal in Lewis acid-catalysed Michael additions relying on the same chiral source.Chemical science · 2021Article
- Synthesis, Structural and Physicochemical Characterization of a Titanium(IV) Compound with the Hydroxamate LigandMolecules (Basel, Switzerland) · 2021Article
- SmIJournal of the American Chemical Society · 2021Article
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5 authors.
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Abstract
Ti(salen) complexes catalyze the asymmetric [3 + 2] cycloaddition of cyclopropyl ketones with alkenes. While high enantioselectivities are achieved with electron-rich alkenes, electron-deficient alkenes are less selective. Herein, we describe mechanistic studies to understand the origins of catalyst and substrate trends in an effort to identify a more general catalyst. Density functional theory (DFT) calculations of the selectivity determining transition state revealed the origin of stereochemical control to be catalyst distortion, which is largely influenced by the chiral backbone and adamantyl groups on the salicylaldehyde moieties. While substitution of the adamantyl groups was detrimental to the enantioselectivity, mechanistic information guided the development of a set of eight new Ti(salen) catalysts with modified diamine backbones. These catalysts were evaluated with four electron-deficient alkenes to develop a three-parameter statistical model relating enantioselectivity to physical organic parameters. This statistical model is capable of quantitative prediction of enantioselectivity with structurally diverse alkenes. These mechanistic insights assisted the discovery of a new Ti(salen) catalyst, which substantially expanded the reaction scope and significantly improved the enantioselectivity of synthetically interesting building blocks.
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