Fungicide-inspired precursors of π-allylpalladium intermediates for palladium-catalyzed decarboxylative cycloadditions

Chemical Science, Год журнала: 2023, Номер 14(11), С. 3024 - 3029

Опубликована: Янв. 1, 2023

Inspired by a fungicide, we designed 5-vinyloxazolidine-2,4-diones as new precursors of π-allylpalladium zwitterionic intermediates and developed palladium-catalyzed asymmetric (5 + 3) cycloaddition with azomethine imines (3 2) 1,1-dicyanoalkenes. Both reactions proceeded smoothly under mild reaction conditions to produce various chiral heterocyclic compounds in high yields excellent enantioselectivities. These results revealed that were type suitable precursor for palladium catalysis will find extensive applications Pd-catalyzed such allylic alkylation.

Язык: Английский

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Palladium-Catalyzed Allylic Alkylation Reactions of Nucleophilic Allenones: Asymmetric Allylic Alkylation, Z/E Divergent Allylic Alkylation, and [5 + 2] Annulation

ACS Catalysis, Год журнала: 2024, Номер 14(13), С. 9940 - 9954

Опубликована: Июнь 19, 2024

Metal-catalyzed allenylic substitution reactions where allenes serve as electrophilic precursors have been recognized a rapid way for novel allene construction. On the contrary, chemistry in which act nucleophiles has far less investigated, especially powerful platform such metal-catalyzed allylic alkylation reactions. We herein describe two unprecedented palladium-catalyzed of an nucleophile. In first reaction, using vinyloxazolidinones allyl precursor, asymmetric allylation trisubstituted allenones worked well to prepare array axially chiral tetrasubstituted allenes. Mechanistic studies and density functional theory (DFT) calculations indicated that weak hydrogen-bonding interaction between acidic C(sp2)–H allenone nitrogen anion π-azaallyl-Pd species is key success stereocontrol. This reaction revealed intriguing reactivity nucleophilic time. second with use allenylethylene carbonates π-oxyallyl-Pd precursors, presented unique under different conditions provide divergent synthetic access (E)- (Z)-allenyl diene products. Interestingly, subsequent sequential intramolecular cyclization/isomerization (Z)-product delivered dihydrooxepine derivatives [5 + 2] annulation

Язык: Английский

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4-Vinylbenzodioxinones as a new type of precursor for palladium-catalyzed (4+3) cycloaddition of azomethine imines

Chemical Communications, Год журнала: 2024, Номер 60(11), С. 1436 - 1439

Опубликована: Янв. 1, 2024

Benzo-fused cyclic carbonates were designed and synthesized as a novel type of precursor π-allylpalladium zwitterionic intermediates.

Язык: Английский

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Palladium-Catalyzed [5 + 4] Cycloaddition of 4-Vinyl-4-Butyrolactones with N-Tosyl Azadienes: Construction of Nine-Membered Ring

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(7), С. 5019 - 5028

Опубликована: Март 19, 2024

In this paper, we reported the palladium-catalyzed formal [5 + 4] cycloaddition reactions between 4-vinyl-4-butyrolactones (VBLs) and azadienes. Under mild reaction conditions, a wide range of benzofuran-fused 9-membered heterocyclic compounds had been provided in moderate to excellent yields with exclusive regioselectivities diastereoselectivities. The practical applicability synthesis was demonstrated through scale-up further transformation.

Язык: Английский

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Palladium-Catalyzed Asymmetric (3 + 2) Cycloaddition of 5-Allenyloxazolidine-2,4-Diones with Barbiturate-Derived Alkenes: Synthesis of Spirobarbiturate-γ-Lactams

Organic Letters, Год журнала: 2023, Номер 25(34), С. 6328 - 6333

Опубликована: Авг. 23, 2023

The 5-allenyloxazolidine-2,4-diones had been synthesized as novel precursors of π-allyl palladium zwitterion and were applied in a palladium-catalyzed enantioselective (3 + 2) annulation by using barbiturate-derived alkenes the reaction partner presence an axially chiral phosphoramidite ligand. This proceeded smoothly under mild conditions, affording highly functionalized spirobarbiturate-γ-lactam derivatives excellent yields along with high diastereo- enantioselectivities. scale-up further transformation product also successful.

Язык: Английский

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Palladium-Catalyzed [3 + 2] Cycloaddition of 4-Vinyl-4-butyrolactones with Ketenes Generated in Situ from Acyl Chlorides: A Method for the Synthesis of Dihydrofurans

Organic Letters, Год журнала: 2024, Номер 26(10), С. 2057 - 2061

Опубликована: Март 1, 2024

In this paper, palladium-catalyzed [3 + 2] cycloaddition of 4-vinyl-4-butyrolactones with ketenes generated from easily available acyl chlorides was achieved. With Pd2(dba)3·CHCl3/XantPhos as the catalyst, reaction proceeded smoothly under mild conditions, affording a series 2,3-dihydrofurans in moderate to high yields. The scale-up and further transformations products are demonstrated, plausible mechanism is proposed well.

Язык: Английский

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Cooperative Pd/Chiral Secondary Amine Enabled Diastereo- and Enantioselective [3 + 2] Cycloannulation: Synthesis of Polysubstituted Cyclopentanes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 17, 2025

A cooperative palladium/chiral amine enabled diastereo- and enantioselective [3 + 2] cycloaddition of π-allyl 1,3-dipoles with α,β-unsaturated aldehydes has been developed. series highly functionalized cyclopentanes bearing three continuous tertiary stereocenters can be facilely efficiently obtained in good to excellent yields (51-97%) synthetically useful enantioselectivity (93-99% ee) under mild reaction conditions. Control experiments HRMS analyses were conducted elucidate the possible mechanism. The utility current method was demonstrated by gram-scale synthesis elaboration products into various cyclopentanes.

Язык: Английский

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Silver-Catalyzed Cascade Approach to Access Fused Pyrazolo-naphthyridine and -isoquinoline Backbones and Investigation of Their Photophysical Properties

ACS Omega, Год журнала: 2025, Номер unknown

Опубликована: Апрель 4, 2025

We describe a novel approach for synthesizing diverse fused heterocyclic compounds by utilizing sequential silver(I) catalyzed reaction between readily obtainable N-amidonaphthyridin ylide and dialkyl acetylenedicarboxylates. This method provides an efficient the selective synthesis of tetracyclic ring-fused 1,6-naphthyridine isoquinoline derivatives, offering exceptional structural diversity. In addition, title constitute interesting class luminophores with tunable emission solvatochromicity.

Язык: Английский

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Palladium-catalyzed [6 + 4] cycloaddition with π-allyl all-carbon 1,6-dipole for the synthesis of ten-membered heterocycles

Organic Chemistry Frontiers, Год журнала: 2023, Номер 11(5), С. 1299 - 1304

Опубликована: Дек. 25, 2023

This work introduces a novel α,α-diester-δ-vinylvalerolactone as dipolar precursor in palladium-catalyzed [6 + 4] cycloaddition reaction with azadienes, resulting the production of ten-membered heterocycles.

Язык: Английский

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Synthesis of biologically active [1,5]diazocino[2,1-b]quinazolinones through [4 + 4] cycloaddition of 2-alkynyl quinazolinones with aza-ortho-quinone methides

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(7), С. 1780 - 1787

Опубликована: Янв. 1, 2023

Biologically active [1,5]diazocino[2,1- b ]quinazolinones were synthesized via base-promoted [4 + 4] cycloaddition of 2-alkynyl quinazolinones with aza- ortho -quinone methides.

Язык: Английский

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