Insights into Cu(I)-Catalyzed Decarboxylation of Propargylic Cyclic Carbonates with Amines: Origins of Regioselectivity and Enantioselectivity

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 21, 2025

Chiral α-functionalized α-amino ketones are sought-after compounds for drug development; however, their acyclic enantioselective synthesis with amines as nucleophiles remains challenging. The catalytic decarboxylation of propargylic cyclic carbonates through metal-allenylidene intermediates has proven to be an efficient route chiral quaternary centers, but its mechanisms require clarification. Herein, we computationally investigate the Cu(I)-catalyzed propargyl aniline [Guo, W. J. Am. Chem. Soc. 2021, 143, 7629-7763]. calculation results elucidate mechanistic details reaction and reveal that enantioselectivity stems from distinct noncovalent interactions in (R)- (S)- transition states, while regioselectivity arises lower steric hindrance attack at C5 versus C1 atom zwitterionic intermediate. IGMH analysis further validates enantiocontrol. theoretical offer insights into nucleophiles, advancing understanding amination aiding development this research field.

Язык: Английский

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Copper‐Catalysed Rearrangement of Cyclic Ethynylethylene Carbonates: Synthetic Applications and Mechanistic Studies

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(14)

Опубликована: Фев. 10, 2023

Transition-metal-catalysed reactions of cyclic ethynylethylene carbonates have been intensively studied because their robustness in new bond formation and diversified molecule construction. Known reaction modes usually involve a substitution step occurring at either the propargylic or terminal alkyne positions. Here, we report an unprecedented pattern which first undergo rearrangement to release allenal intermediates, subsequently react with diverse nucleophiles furnish synthetically useful allylic allenols, phosphorus ylides, cyclopropylidene ketones through addition process rather than pathway. The products enable various further transformations, mechanistic studies theoretical calculations reveal that does not proceed via semipinacol type [1,2]-hydride shift, but base-mediated deprotonation as key induce rearrangement.

Язык: Английский

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CuI-catalyzed decarboxylative highly regioselective phosphonylation of terminal alkyne-substituted cyclic carbonates/carbamates to access 4-phosphonyl 2,3-allenols/2,3-allenamines

Tetrahedron, Год журнала: 2021, Номер 104, С. 132606 - 132606

Опубликована: Дек. 13, 2021

Язык: Английский

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Copper-catalyzed allenynylative C–P coupling of diynylic acetates with hydrophosphoryl compounds leading to phosphorylated allenynes

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(17), С. 4836 - 4841

Опубликована: Янв. 1, 2024

A copper-catalyzed allenynylative C–P coupling reaction between diynylic acetates and hydrophosphoryl compounds is developed via nucleophilic interception of copper-cumulenylidene intermediates.

Язык: Английский

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Copper-Catalyzed Enantioselective O,S-Rearrangement of Propargylic Xanthates: Efficient Synthesis of Chiral Propargylic Sulfur Compounds

ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 13283 - 13290

Опубликована: Авг. 21, 2024

A base-free, copper-catalyzed enantioselective O,S-rearrangement of propargylic xanthates has been developed to enable efficient synthesis chiral sulfur compounds in high yields with good enantioselectivities. This method allows for the use a variety containing primary, secondary, and tertiary alkyl substituents tolerates broad range functional groups. The synthetic utility this demonstrated through various downstream transformations resulting products diverse enantioenriched organosulfur compounds. Mechanistic studies suggest pseudo-intramolecular nucleophilic attack anion copper–allenylidene species is likely involved C–S bond formation.

Язык: Английский

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Migratory insertion of copper-allenylidene from propargyl ester

Chemical Communications, Год журнала: 2022, Номер 58(32), С. 4969 - 4972

Опубликована: Янв. 1, 2022

The highly efficient copper-catalyzed homo-dimerization and cross-coupling of propargyl esters have been developed. Various 1-en-3,5-diynes, [5]cumulenes 1,3-diynes were successfully furnished via the copper-allenylidene intermediates with moderate to excellent yields. Migratory insertion is proposed as key step achieve selectivity at carbene carbon copper-allenylidene.

Язык: Английский

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A palladium-catalyzed decarboxylative (5 + 5) cyclization reaction of vinyloxazolidine-2,4-diones: access to ten-membered N,O-containing heterocycles

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(15), С. 4131 - 4137

Опубликована: Янв. 1, 2024

A palladium-catalyzed decarboxylative (5 + 5) cyclization reaction of vinyloxazolidine-2,4-diones for the synthesis ten-membered N,O-containing heterocycles is disclosed.

Язык: Английский

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Ru(II)-Catalyzed Decarboxylative (4 + 2)-Annulation of Benzoic Acids and Benzamides with Propargyl Cyclic Carbonates

Organic Letters, Год журнала: 2024, Номер 26(36), С. 7590 - 7595

Опубликована: Сен. 3, 2024

Propargyl cyclic carbonates have emerged as versatile precursors in synthetic chemistry. However, their reactivity has so far been limited to transition metal-catalyzed substitution and cyclization reactions. Herein, we illustrate the successful employment of propargyl coupling partners Ru(II)-catalyzed C-H annulation benzoic acids benzamides. This approach allowed us access a broad range biologically relevant isocoumarin isoquinolinone derivatives good excellent yields, utilizing bench-stable easily accessible precursors. Preliminary mechanistic studies indicated that metalation step is both reversible rate-determining reaction pathway. Furthermore, utility developed methodology illustrated by scale-up postfunctionalization experiments.

Язык: Английский

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Synthesis of Polydiynes via an Unexpected Dimerization/Polymerization Sequence of C3 Propargylic Electrophiles

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(19), С. 8807 - 8817

Опубликована: Май 6, 2022

Here, we describe the unexpected discovery of a Cu-catalyzed condensation polymerization reaction propargylic electrophiles (CPPE) that transforms simple C3 building blocks into polydiynes C6 repeating units. This was achieved by system composed copper acetylide initiator and an electron-rich phosphine ligand. Alkyne polymers (up to 33.8 kg/mol) were produced in good yields exclusive regioselectivity with high functional group compatibility. Hydrogenation product afforded new polyolefin-type backbone, while base-mediated isomerization led type dienyne-based electron-deficient conjugated polymer. Mechanistic studies revealed α–α selective dimerization pathway unit, followed situ organocopper-mediated chain-growth propagation. These insights not only provide important understanding CPPE C3, C4, monomers general but also lead significantly improved synthesis from simpler starting materials handles for incorporation α-end group.

Язык: Английский

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Copper‐Catalyzed α,β‐Regioselective (2+4) Cycloaddition of Propargylic Esters

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(46)

Опубликована: Сен. 26, 2023

Abstract A copper‐catalyzed α,β‐regioselective (2+4) cycloaddition of propargylic esters with o ‐hydroxyphenyl substituted secondary phosphine oxides (SPOs) was established, which afforded a series phosphorus‐containing six‐membered heterocycles in high yields. This reaction represents the first (2+n) via intermediates copper‐allenylidenes, will enrich chemistry and copper‐allenylidenes. Moreover, this work also application SPOs as 1,4‐dinucleophiles cycloadditions, provides useful protocol for synthesis potential bioactivity.

Язык: Английский

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