ArticleJournal of the American Chemical Society2012
Scope and mechanistic analysis of the enantioselective synthesis of allenes by rhodium-catalyzed tandem ylide formation/[2,3]-sigmatropic rearrangement between donor/acceptor carbenoids and propargylic alcohols.
Article in Journal of the American Chemical Society, 2012. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 29 papers.
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Who cites it
29 citing papers in PubMed, 196 citations in OpenAlex.
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- Chiral ruthenium complex/PhScience advances · 2025Article
- Visible Light-Induced Reactions of Diazo Compounds and Their Precursors.Chemical reviews · 2024Review
- Rhodium(II)-Catalyzed Asymmetric Cyclopropanation and Desymmetrization of [2.2]Paracyclophanes.ACS catalysis · 2024Article
- Stereoselectivity control in Rh-catalyzed β-OH elimination for chiral allene formation.Nature communications · 2023Article
- Three-Component Approach to Densely Functionalized Trifluoromethyl Allenols by Asymmetric Organocatalysis.Journal of the American Chemical Society · 2023Article
- X-H Bond Insertion Promoted by Heterogeneous Dirhodium Metal-Organic Cage with Alkynes as Safe Carbene Precursors.Molecules (Basel, Switzerland) · 2023Article
- Recent advances in metal-catalysed asymmetric sigmatropic rearrangements.Chemical science · 2022Review
- Kinetic resolution of racemic tertiary allylic alcohols through SChemical science · 2022Article
- Enyne diketones as substrate in asymmetric Nazarov cyclization for construction of chiral allene cyclopentenones.Nature communications · 2022Article
- Catalytic rearrangements of onium ylides in aromatic systems.Organic & biomolecular chemistry · 2022Review
- Tunable Gold-catalyzed Reactions of Propargyl Alcohols and Aryl Nucleophiles.ChemistryOpen · 2022Article
- Experimental and Theoretical DFT Investigations in the [2,3]-Wittig-Type Rearrangement of Propargyl/Allyl-Oxy-Pyrazolones.Molecules (Basel, Switzerland) · 2021Article
- Catalyst-Controlled Regiodivergence in Rearrangements of Indole-Based Onium Ylides.Journal of the American Chemical Society · 2021Article
- Deciphering the Chameleonic Chemistry of Allenols: Breaking the Taboo of a Onetime Esoteric Functionality.Chemical reviews · 2021Article
- Recent Perspectives on Rearrangement Reactions of Ylides via Carbene Transfer Reactions.Chemistry (Weinheim an der Bergstrasse, Germany) · 2021Review
- Isothiourea-Catalyzed Acylative Kinetic Resolution of Tertiary α-Hydroxy Esters.Angewandte Chemie (International ed. in English) · 2020Article
- Copper-catalyzed 1,4-alkylarylation of 1,3-enynes with masked alkyl electrophiles.Chemical science · 2019Article
- Enantiodivergent Synthesis of Allenes by Point-to-Axial Chirality Transfer.Angewandte Chemie (International ed. in English) · 2018Article
- Catalytic asymmetric trifluoromethylthiolation via enantioselective [2,3]-sigmatropic rearrangement of sulfonium ylides.Nature chemistry · 2017Article
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6 authors at 3 institutions in 1 country.
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Abstract
Rhodium-catalyzed reactions of tertiary propargylic alcohols with methyl aryl- and styryldiazoacetates result in tandem reactions, consisting of oxonium ylide formation followed by [2,3]-sigmatropic rearrangement. This process competes favorably with the standard O-H insertion reaction of carbenoids. The resulting allenes are produced with high enantioselectivity (88-98% ee) when the reaction is catalyzed by the dirhodium tetraprolinate complex, Rh(2)(S-DOSP)(4). Kinetic resolution is possible when racemic tertiary propargylic alcohols are used as substrates. Under the kinetic resolution conditions, the allenes are formed with good diastereoselectivity and enantioselectivity (up to 6.1:1 dr, 88-93% ee), and the unreacted alcohols are enantioenriched to 65-95% ee. Computational studies reveal that the high asymmetric induction is obtained via an organized transition state involving a two-point attachment: ylide formation between the alcohol oxygen and the carbenoid and hydrogen bonding of the alcohol to a carboxylate ligand. The 2,3-sigmatropic rearrangement proceeds through initial cleavage of the O-H bond to generate an intermediate with close-lying open-shell singlet, triplet, and closed-shell singlet electronic states. This intermediate would have significant diradical character, which is consistent with the observation that the 2,3-sigmatropic rearrangement is favored with donor/acceptor carbenoids and more highly functionalized propargylic alcohols.
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