Cu-Catalyzed Diastereo- and Enantioselective Synthesis of Borylated Cyclopropanes with Three Contiguous Stereocenters

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration cyclopropenes, less reactive alkyl iodides as electrophiles, for the efficient tetra-substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, broad substrate scope, good functional group tolerance, affording array chiral in to high yields excellent enantioselectivities. Detailed mechanistic experiments kinetic studies were conducted elucidate reaction pathway rate-determining step reaction. DFT calculations revealed that π···π stacking interaction between phenyl groups on phosphorus ligand, along smaller distortion CuL-Bpin part, contributed The synthetic utility was showcased by facile some valuable centers.

Language: Английский

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Asymmetric Radical Bicyclization for Stereoselective Construction of Tricyclic Chromanones and Chromanes with Fused Cyclopropanes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(21), P. 11622 - 11632

Published: May 2, 2023

Asymmetric radical bicyclization processes have been developed via metalloradical catalysis (MRC) to stereoselectively construct chiral chromanones and chromanes bearing fused cyclopropanes. Through optimization of a versatile

Language: Английский

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Diastereoselective Synthesis of Cyclopropanes from Carbon Pronucleophiles and Alkenes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 16, 2023

Abstract Cyclopropanes are desirable structural motifs with valuable applications in drug discovery and beyond. Established alkene cyclopropanation methods give rise to cyclopropanes a limited array of substituents, difficult scale, or both. Herein, we disclose new cyclopropane synthesis through the formal coupling abundant carbon pronucleophiles unactivated alkenes. This strategy exploits dicationic adducts derived from electrolysis thianthrene presence substrates. We find that these dielectrophiles undergo methylene via alkenyl thianthrenium intermediates. protocol is scalable, proceeds high diastereoselectivity, tolerates diverse functional groups on both pronucleophile partners. To validate utility this procedure, prepared an substituted analogs established en route multiple pharmaceuticals.

Language: Английский

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Modular Access tometa-Substituted Benzenes via Mo-Catalyzed Intermolecular Deoxygenative Benzene Formation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(16), P. 8781 - 8787

Published: March 17, 2023

The substituted benzene derivatives are essential to organic synthesis, medicinal chemistry, and material science. However, the 1,3-di- 1,3,5-trisubstituted benzenes far less prevalent in small-molecule drugs than other substitution patterns, likely due lack of robust, efficient, convenient synthetic methods. Here, we report a Mo-catalyzed intermolecular deoxygenative benzene-forming reaction readily available ynones allylic amines. A wide range unsymmetric unfunctionalized were obtained up 88% yield by using commercially molybdenum catalyst. potential method was further illustrated transformations, scale-up derivatization bioactive molecules. Preliminary mechanistic studies suggested that this process might proceed through aza-Michael addition/[1,5]-hydride shift/cyclization/aromatization cascade. This strategy not only provided facile, modular approach various meta-substituted but also demonstrated catalysis challenging cross-coupling reactions.

Language: Английский

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Redox Approaches to Carbene Generation in Catalytic Cyclopropanation Reactions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 16, 2024

Abstract Transition metal‐catalyzed carbene transfer reactions have a century‐old history in organic chemistry and are primary method for the synthesis of cyclopropanes. Much work this field has focused on use diazo compounds related precursors, which can fragment to catalyst with concomitant loss stable byproduct. Despite utility approach, there persistent limitations scope viable carbenes, most notably those lacking stabilizing substituents. By coupling two‐electron redox cycles, it is possible expand available starting materials that be used as precursors. In Minireview, we discuss emerging catalytic reductive cyclopropanation using either gem ‐dihaloalkanes or carbonyl compounds. This strategy inspired by classic stoichiometric transformations, such Simmons–Smith Clemmensen reduction, but instead entails formation catalytically generated transition metal carbenoid. We also present recent efforts generate carbenes directly from methylene (CR 2 H ) groups via formal 1,1‐dehydrogenation. These currently restricted substrates containing electron‐withdrawing substituents, serve facilitate deprotonation subsequent oxidation anion.

Language: Английский

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Catalytic Diastereo‐ and Enantioselective Cyclopropanation of gem‐Dihaloalkanes and Terminal Olefins

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: May 11, 2023

Chiral cyclopropane derivatives are essential in synthetic chemistry and drug discovery. Their synthesis commonly relies on asymmetric cyclopropanation of diazo compounds, potentially explosive needing stabilizing substituents. Thus, catalytic transformations non-stabilized carbenes or carbenoids remain a formidable challenge. Herein, we report the unprecedented chromium-catalyzed readily available gem-dihaloalkanes terminal olefins. Distinct from previous approaches, serve as suitable precursors for carbenoids, furnishing various functionalized chiral cyclopropanes. Mechanistic studies, including radical trapping, non-linear effect, UV/Vis spectroscopy, provide insights into process, featuring radical-polar crossover.

Language: Английский

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Catalytic Intermolecular Deoxygenative Coupling of Carbonyl Compounds with Alkynes by a Cp*Mo(II)-Catalyst

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5605 - 5613

Published: Feb. 14, 2024

Carbonyl is highly accessible and acts as an essential functional group in chemical synthesis. However, the direct catalytic deoxygenative functionalization of carbonyl compounds via a putative metal carbene intermediate formidable challenge due to requirement high activation energy for cleavage strong C═O double bonds. Here, we report class bench stable readily available Cp*Mo(II)-complexes efficient deoxygenation catalysts that could catalyze intermolecular coupling with alkynes. Enabled by this powerful Cp*Mo(II)-catalyst, various valuable heteroarenes (10 different classes) were obtained generally good yields remarkable chemo- regioselectivities. Mechanistic studies suggested reaction might proceed sequence bonds cleavage, carbene-alkyne metathesis, cyclization, aromatization processes. This strategy not only provided general platform rapid preparation but also opened new window applications Cp*Mo(II)-catalysts organic

Language: Английский

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Cyano migration-mediated radical-polar crossover cyclopropanation

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 3, 2024

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Visible-light-mediated deoxygenative transformation of 1,2-dicarbonyl compounds through energy transfer process

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Oct. 25, 2024

Language: Английский

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Recent developments and applications of solid membrane in chiral separation

Journal of Chromatography A, Journal Year: 2025, Volume and Issue: 1743, P. 465652 - 465652

Published: Jan. 2, 2025

Language: Английский

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