An update on chiral phosphoric acid organocatalyzed stereoselective reactions

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(17), С. 3477 - 3502

Опубликована: Янв. 1, 2023

This review article presents an in-depth analysis of the strategies and methodologies for using chiral phosphoric acids as organocatalysts in asymmetric syntheses from recent literature.

Язык: Английский

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Asymmetric total synthesis of polycyclic xanthenes and discovery of a WalK activator active against MRSA

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 13, 2024

The development of new antibiotics continues to pose challenges, particularly considering the growing threat multidrug-resistant Staphylococcus aureus. Structurally diverse natural products provide a promising source antibiotics. Herein, we outline concise approach for collective asymmetric total synthesis polycyclic xanthene myrtucommulone D and five related congeners. strategy involves rapid assembly challenging benzopyrano[2,3-a]xanthene core, highly diastereoselective establishment three contiguous stereocenters through retro-hemiketalization/double Michael cascade reaction, Mitsunobu-mediated chiral resolution with high optical purity broad substrate scope. Quantum mechanical calculations insight into stereoselective construction mechanism stereocenters. Additionally, this work leads discovery an antibacterial agent against both drug-sensitive drug-resistant S. This compound operates unique that promotes bacterial autolysis by activating two-component sensory histidine kinase WalK. Our research holds potential future drug development.

Язык: Английский

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Catalyst-controlled regiodivergence and stereodivergence in formal cross-[4+2] cycloadditions: The unique effect of bismuth(III)

Science Advances, Год журнала: 2025, Номер 11(13)

Опубликована: Март 26, 2025

The [4+2] cycloaddition is crucial for constructing six-membered rings in pharmaceuticals and natural products. Cross-[4+2] cycloadditions offer greater product diversity than traditional diene-dienophile reactions due to multiple possible pathways. However, precise control over regio- stereoselectivity various isomers remains a great challenge. This study reports catalyst-controlled regiodivergent formal cross-cycloadditions of acyclic dienes enones, significantly enhancing access diverse pyrazole-fused spirooxindoles. Chiral phosphoric acid (CPA) catalysis enables endoselective cycloadditions, while Bi(III) with CPA ligand yields [2+4] products high stereoselectivity. A Claisen rearrangement the adduct produces exo-selective product, further increasing stereochemical enabling synthesis six stereo-isomers from single substrate set. DFT calculations reveal that reverses regioselectivity by repositioning reactants pocket stabilizing enone oxygen’s negative charge. In addition, 3as demonstrates therapeutic potential against triple-negative breast cancer, an IC 50 8.5 μM MDA-MB-453 cells.

Язык: Английский

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Enantioselective and Regiodivergent Synthesis of Dihydro-1,2-oxazines from Triene-Carbamates via Chiral Phosphoric Acid-Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(48), С. 26504 - 26515

Опубликована: Ноя. 27, 2023

Conjugated trienes are fascinating building blocks for the rapid construction of complex polycyclic compounds. However, limited success has been achieved due to challenging regioselectivity control. Herein, we report an enantio- and diastereoselective process allowing regioselectively control functionalization NH-triene-carbamates. Synthesis chiral cis-3,6-dihydro-2H-1,2-oxazines is by a phosphoric acid catalyzed Nitroso-Diels-Alder cycloaddition involving [(1E,3E,5E)-hexa-1,3,5-trien-1-yl]carbamates. Moreover, modular access three different regioisomers with excellent diastereoselectivities high enantioselectivities obtained careful choice reaction conditions. A computational study reveals that influenced steric demand substituents at 6-position triene, as well noncovalent interactions between two partners. Utility each regioisomeric cycloadduct highlighted variety synthetic transformations.

Язык: Английский

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Regio- and stereo-selective synthesis of β-phenylthio enamides via intramolecular 1,2-thiol migration

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(9), С. 2442 - 2447

Опубликована: Янв. 1, 2024

An efficient and novel method for the direct synthesis of β-phenylthio enamides via intramolecular 1,2-thiol migration has been developed.

Язык: Английский

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Enantioselective Construction of Polycyclic Chromanes through Organocatalytic Sequential Quintuple Reaction via One‐Pot Step‐Wise Procedure

Chinese Journal of Chemistry, Год журнала: 2024, Номер 42(18), С. 2197 - 2202

Опубликована: Май 14, 2024

Comprehensive Summary An efficient and highly stereoselective synthetic method to access polycyclic chromanes has been achieved through organocatalyzed one‐pot step‐wise reactions involving 2‐hydroxycinnamaldehydes, 2‐aminochalcones, malononitrile as substrates. The underwent a quintuple process by aza‐Michael/Michael/Knoevenagel/oxa‐Michael/aldol‐type reaction in sequence give products bearing 3 new generated rings 5 chiral centers moderate quantitative yields with excellent stereoselectivities. A novel retro‐reaction mechanism was discovered the transformations of products.

Язык: Английский

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Domino Doyle‐Kirmse/Claisen‐Thioimidate Rearrangements: Access to 2‐Aminobuta‐1,3‐diene Derivatives of Benzazole‐2‐thiones

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(19), С. 4078 - 4083

Опубликована: Июль 26, 2024

Abstract A domino sequence consisting of a rhodium‐catalyzed Doyle‐Kirmse rearrangement followed by Claisen‐thioimidate has been developed. This type thio‐Claisen represents the first example reported in homoallenylsulfenyl series. The involves 2‐propargylsulfenyl benzazoles and diazoesters, affording N ‐butadienyl substituted benzazole‐2‐thiones as mixture Z E isomers, yields ranging from 12% to quantitative (32 examples). method provides rapid access new family highly polyfunctionalized 2‐aminobuta‐1,3‐dienes with potential synthetic applications.

Язык: Английский

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Six-membered ring systems: With O and/or S atoms

Progress in heterocyclic chemistry, Год журнала: 2024, Номер unknown, С. 421 - 484

Опубликована: Янв. 1, 2024

Язык: Английский

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Nickel‐Catalyzed Stereoselective Migratory Carboboration of 1,4‐Cyclohexadiene^†

Chinese Journal of Chemistry, Год журнала: 2023, Номер unknown

Опубликована: Окт. 3, 2023

Comprehensive Summary Multi‐substituted cyclohexanes play a crucial role as scaffolds in bioactive compounds. While significant progress has been made synthesizing substituted cyclohexanes, methods for the stereoselective assembly of 1,3‐disubstituted remain scarce. This study presents novel approach involving nickel catalysis to achieve carboboration 1,4‐cyclohexadiene. innovative process allows simultaneous introduction boron group and an aryl or alkyl fragment into 1,4‐cyclohexadiene framework under mild conditions, with exclusive regioselectivity excellent cis configuration. The resulting products feature double carbon bond incorporation group, offering potential subsequent transformations downstream applications.

Язык: Английский

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Chiral Phosphoric Acid-Catalyzed Diels–Alder Reaction of 2-Trifluoroacetamido-1,3-Dienes and Enones

Synfacts, Год журнала: 2023, Номер 19(02), С. 0184 - 0184

Опубликована: Янв. 17, 2023

Key words Diels–Alder reaction - cycloaddition 2-amino-1,3-dienes enones chiral phosphoric acid

Язык: Английский

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