ArticleNature chemistry2018
Mechanism-based enhancement of scope and enantioselectivity for reactions involving a copper-substituted stereogenic carbon centre.
Article in Nature chemistry, 2018. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 32 papers.
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Who cites it
32 citing papers in PubMed.
- Kinetics and Mechanism of Enantioselective Cu-Catalyzed Alcohol Silylation.Journal of the American Chemical Society · 2025Article
- Enantioselective Synthesis of 2,3-Disubstituted Azetidines via Copper-Catalyzed Boryl Allylation of Azetines.Journal of the American Chemical Society · 2025Article
- Tandem Diboration-Protoboration of Terminal Alkynes: A Practical Route to α-Substituted Alkenyl Boronates.Synlett : accounts and rapid communications in synthetic organic chemistry · 2025Article
- Recent advances in allylation of chiral secondary alkylcopper species.Beilstein journal of organic chemistry · 2025Review
- Wingtip-Flexible N-Heterocyclic Carbenes: Unsymmetrical Connection between IMes and IPr.Angewandte Chemie (International ed. in English) · 2024Article
- Stereoselective Copper-Catalyzed Olefination of Imines.Angewandte Chemie (International ed. in English) · 2024Article
- A general approach to stereospecific Pd-catalyzed cross-coupling reactions of benzylic stereocenters.Chemical science · 2023Article
- Catalytic Lewis Base Additive Enables Selective Copper-Catalyzed Borylative α-C-H Allylation of Alicyclic Amines.Journal of the American Chemical Society · 2022Article
- Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides.Angewandte Chemie (International ed. in English) · 2022Article
- Generation of Axially Chiral Fluoroallenes through a Copper-Catalyzed Enantioselective β-Fluoride Elimination.Journal of the American Chemical Society · 2021Article
- Sulfonate N-Heterocyclic Carbene-Copper Complexes: Uniquely Effective Catalysts for Enantioselective Synthesis of C-C, C-B, C-H, and C-Si Bonds.Angewandte Chemie (International ed. in English) · 2020Review
- Copper-Catalyzed Borylative Couplings with C-N Electrophiles.Angewandte Chemie (International ed. in English) · 2020Review
- Copper-catalyzed functionalization of enynes.Chemical science · 2020Review
- Asymmetric synthesis of γ-chiral borylalkanesChemical science · 2020Article
- Beyond Carbon: Enantioselective and Enantiospecific Reactions with Catalytically Generated Boryl- and Silylcopper Intermediates.ACS central science · 2020Review
- Evidence for Simultaneous Dearomatization of Two Aromatic Rings under Mild Conditions in Cu(I)-Catalyzed Direct Asymmetric Dearomatization of Pyridine.Journal of the American Chemical Society · 2020Article
- Lessons in Strain and Stability: Enantioselective Synthesis of (+)-[5]-Ladderanoic Acid.Angewandte Chemie (International ed. in English) · 2020Article
- Cascade CuH-Catalysed Conversion of Alkynes to Enantioenriched 1,1-Disubstituted Products.Nature catalysis · 2020Article
- 2-Azadienes as Enamine Umpolung Synthons for the Preparation of Chiral Amines.Synlett : accounts and rapid communications in synthetic organic chemistry · 2019Article
- Regio- and Enantioselective Synthesis of 1,2-Diamine Derivatives by Copper-Catalyzed Hydroamination.Organic letters · 2019Article
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5 authors.
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Abstract
A rapidly emerging set of catalytic reactions involves intermediates that contain a copper-substituted stereogenic carbon centre. Here, we demonstrate that an intimate understanding of this distinction provides ways for addressing limitations in reaction scope and explaining why unexpected variations in enantioselectivity often occur. By using catalytic enantioselective Cu-boryl addition to alkenes as the model process, we elucidate several key mechanistic principles. We show that higher electrophile concentration can lead to elevated enantioselectivity. This is because diastereoselective Cu-H elimination may be avoided and/or achiral Cu-boryl intermediates can be converted to allyl-B(pin) rather than add to an alkene. We illustrate that lower alkene amounts and/or higher chiral ligand concentration can minimize the deleterious influence of achiral Cu-alkyl species, resulting in improved enantiomeric ratios. Moreover, and surprisingly, we find that enantioselectivities are higher with the less reactive allylphenyl carbonates as chemoselective copper-hydride elimination is faster with an achiral Cu-alkyl species.
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