Synthesis, Год журнала: 2023, Номер 56(03), С. 389 - 398
Опубликована: Авг. 16, 2023
Abstract This short review summarizes the recent impressive developments on high-order dipolar annulations (HODAs) of donor–acceptor cyclopropanes (DACs) and cyclobutanes (DABs) to afford medium-sized (hetero)cycles. 1 Introduction 2 (3+m) (m > 3) Annulations Donor–Acceptor Cyclopropanes 2.1 (3+4) 2.2 (3+5) 3 (4+m) 2) Cyclobutanes 4 Conclusion
Язык: Английский
Chemical Communications, Год журнала: 2023, Номер 59(9), С. 1233 - 1236
Опубликована: Янв. 1, 2023
Herein, a palladium-catalyzed general synthetic strategy to access an attractive and decorated set of chiral spiro derivatives benzoxazine compounds is unveiled utilizing vinyl benzoxazinanones reacted with pyrazolone 4,5-diones, which extends the application ketones. This asymmetric catalytic [4+2] cycloaddition reaction demonstrates broad substrate scope functional group tolerance in yields up 76% 96% ee. A facile scale-up straightforward conversion diversely substituted products verify utility this method.
Язык: Английский
Процитировано
16
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
Процитировано
6
Advanced Science, Год журнала: 2024, Номер 11(31)
Опубликована: Июнь 17, 2024
Abstract Oxazocines are key structural intermediates in the synthesis of natural products and pharmaceutical molecules. However, oxazocines especially a highly enantioselective manner, is long‐standing formidable challenge due to unfavorable energetics involved cyclization. Herein, series new PNP‐Ligand P ‐chiral stereocenter first designed synthesized, called MQ‐Phos , successfully applied it Pd‐catalyzed higher‐order formal [4+4]‐cycloaddition α β ‐unsaturated imines with 2‐(hydroxymethyl)‐1‐arylallyl carbonates. The reaction features mild conditions, excellent regio‐ enantiocontrol broad substrate scope (54 examples). Various medium‐sized rings can be afforded moderate yields (up 92%) enantioselectivity 99% ee). newly developed critical for ring catalytic reactivity enantioselectivity.
Язык: Английский
Процитировано
6
ACS Catalysis, Год журнала: 2024, Номер 14(20), С. 15743 - 15750
Опубликована: Окт. 9, 2024
Medium-sized rings are important structural units in organic molecules of significant interest. However, their efficient synthesis, especially a highly enantioselective manner, has been formidable challenge. Herein, we report an synthesis medium-sized aza-rings by Z-retentive asymmetric allylic substitution-enabled intermolecular cascade cyclization via iridium/cinchona dual catalysis. The reaction was performed under mild conditions and with good functional group tolerance. Various nine- to eleven-membered can be afforded moderate high yields (up 98%) enantioselectivities 93% ee). utilization both Z-linear dipole precursor binary catalyst is critical for the desired reactivity.
Язык: Английский
Процитировано
6
Chinese Journal of Organic Chemistry, Год журнала: 2022, Номер 42(10), С. 3051 - 3051
Опубликована: Янв. 1, 2022
Chiral heterocyclic compounds are an important class of chiral substances, which widespread in many drugs, pesticides and catalysts.Therefore, the efficient asymmetric synthesis these becomes a research hotspot organic synthesis.Transition metal-catalyzed cyclization with heteroatom-dipole precursors is method to construct frameworks.Among them, designed based on transition allyl or propargyl substitutions have been extensively studied past two decades occupied role this field.The cyclizations introduced detail.The advantages existing problems current methods analyzed, would provide useful reference for researchers related fields.
Язык: Английский
Процитировано
22
Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(3)
Опубликована: Ноя. 15, 2022
Ring-opening transformations of donor-acceptor (D-A) cyclopropanes enable the rapid assembly complex molecules. However, enantioselective formation chiral quaternary stereocenters using substrates bearing two different acceptors remains a challenge. Herein, we describe first palladium-catalyzed highly diastereo- and (3+2) cycloaddition vinyl electron-withdrawing groups, subset D-A cyclopropanes. The key to success this reaction is remote stereoinduction through hydrogen bond from ligands, which thereby addressed aforementioned A variety five-membered heterocycles were produced in good yields with high stereoselectivity (up 99 % yields, : 1 er >19 dr). In-depth mechanistic investigations, including control experiments theoretical calculations, revealed origin importance H-bonding stereocontrol.
Язык: Английский
Процитировано
20
Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(21), С. 2825 - 2831
Опубликована: Июнь 25, 2023
Comprehensive Summary We developed a novel Pd‐catalyzed [4 + 4] cycloaddition of (benzo)furan‐derived azadienes with homo‐TMM all‐carbon 1,4‐dipoles in situ generated from α ‐allyl malonate derivatives, affording an array benzofuro[3,2‐ b ]azocines and furo[3,2‐ good to excellent yields (up 96%) exclusive regioselectivities. This methodology featured mild reaction conditions functional group tolerance. The synthetic utility was demonstrated by gram‐scale reaction. Furthermore, the catalytic asymmetric version has also been explored.
Язык: Английский
Процитировано
13
Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(6)
Опубликована: Дек. 15, 2023
Abstract We report herein an unprecedented enantioselective (4+4) cycloaddition of simple 1,3‐dienes with azadienes for the construction fused eight‐membered N ‐heterocycles. In this transformation, π‐Lewis basic Pd(0) catalyst achieves activation to induce nucleophilic addition followed by ring cyclization via a selective terminal allylic substitution. Furthermore, highly efficient and diastereoselective derivatizations rings provide facile access diverse enantiopure tetra‐ hexacyclic compounds potential application in medicinal chemistry.
Язык: Английский
Процитировано
13
Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)
Опубликована: Март 18, 2023
Metal-polarized aza-ortho-quinone methides (aza-o-QMs) are a unique and efficient handle for azaheterocycle synthesis. Despite great achievements, the potential of these reactive intermediates has not yet been fully exploited, especially new reaction modes. Herein, we disclosed an unprecedented dearomatization process metal-polarized aza-o-QMs, affording transient dearomatized spiroaziridine intermediates. Based on this serendipity, accomplished three sequential dearomatization-rearomatization reactions benzimidazolines with aza-sulfur ylides, enabling divergent synthesis bis-nitrogen heterocycles high efficiency flexibility. Moreover, experimental theoretical studies were performed to explain proposed mechanisms observed selectivity. Further cellular evaluation dibenzodiazepine products identified hit compound antitumor drugs.
Язык: Английский
Процитировано
12
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
Процитировано
12