Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp³)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(20)

Опубликована: Март 19, 2024

Abstract Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp 3 )−H functionalization, among which Os(II)/Salox species is found be most efficient for precise stereocontrol in realizing amidation. As exemplified by enantioenriched pyrrolidinone synthesis, such tailored catalyst efficiently enables an intramolecular site‐/enantioselective amidation γ‐position dioxazolone substrates, benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording corresponding γ‐lactam products with good er values (up 99 : 1) diverse functionality (>35 examples). The unique performance advantage developed system terms catalytic energy profile induction has further clarified integrated experimental computational studies.

Язык: Английский

---

Selective C–H Iodination of Weinreb Amides and Benzamides through Iridium Catalysis in Solution and under Mechanochemical Conditions

Organic Letters, Год журнала: 2023, Номер 26(14), С. 2800 - 2805

Опубликована: Ноя. 6, 2023

The acid mediated ortho-iodination of Weinreb amides using a readily available catalyst is described. selective amides, challenging substrates in directed C–H activations, and also benzamides achieved. process works under mild conditions tolerates air moisture, having great potential for industrial applications. methodology can be applied mechanochemical maintaining the reaction outcome selectivity.

Язык: Английский

---

Carboxyl group assisted isodesmicmeta-C–H iodination of phenethylamines, benzylamines, and 2-aryl anilines

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(15), С. 3760 - 3765

Опубликована: Янв. 1, 2023

Remote isodesmic meta -C–H iodination of phenethylamines, benzylamines, and 2-aryl anilines was enabled by an alkyl carboxyl group.

Язык: Английский

---

Hyperconjugation‐Driven Isodesmic Reaction of Indoles and Anilines: Reaction Discovery, Mechanism Study, and Antitumor Application

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(47)

Опубликована: Авг. 23, 2024

Abstract Isodesmic reactions, in which chemical bonds are redistributed between substrates and products, provide a general powerful strategy for both biological synthesis. However, most isodesmic reactions involve either metathesis or functional‐group transfer. Here, we serendipitously discovered novel reaction of indoles anilines that proceeds intramolecularly under weakly acidic conditions. In this process, the five‐membered ring indole motif is broken new constructed on aniline side, accompanied by formation motif. Mechanistic studies revealed pivotal role σ→π* hyperconjugation nitrogen atom driving unusual reaction. Furthermore, successfully synthesized diverse series polycyclic derivatives; among quinolines, potential antitumor agents were identified using cellular vivo experiments, thereby demonstrating synthetic utility developed methodology.

Язык: Английский

---

Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp³)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development

Angewandte Chemie, Год журнала: 2024, Номер 136(20)

Опубликована: Март 19, 2024

Abstract Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp 3 )−H functionalization, among which Os(II)/Salox species is found be most efficient for precise stereocontrol in realizing amidation. As exemplified by enantioenriched pyrrolidinone synthesis, such tailored catalyst efficiently enables an intramolecular site‐/enantioselective amidation γ‐position dioxazolone substrates, benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording corresponding γ‐lactam products with good er values (up 99 : 1) diverse functionality (>35 examples). The unique performance advantage developed system terms catalytic energy profile induction has further clarified integrated experimental computational studies.

Язык: Английский

---

Palladium-catalyzed epoxidation of olefins using electrophiles as oxidizing agents

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(17), С. 4689 - 4696

Опубликована: Янв. 1, 2024

The development of palladium-catalysed olefin epoxidation reactions using electrophilic reagents as oxidants: modular synthesis oxazolines. efficient esters, alcohols and halogen-containing products was achieved.

Язык: Английский

---

Hyperconjugation‐Driven Isodesmic Reaction of Indoles and Anilines: Reaction Discovery, Mechanism Study, and Antitumor Application

Angewandte Chemie, Год журнала: 2024, Номер 136(47)

Опубликована: Авг. 23, 2024

Abstract Isodesmic reactions, in which chemical bonds are redistributed between substrates and products, provide a general powerful strategy for both biological synthesis. However, most isodesmic reactions involve either metathesis or functional‐group transfer. Here, we serendipitously discovered novel reaction of indoles anilines that proceeds intramolecularly under weakly acidic conditions. In this process, the five‐membered ring indole motif is broken new constructed on aniline side, accompanied by formation motif. Mechanistic studies revealed pivotal role σ→π* hyperconjugation nitrogen atom driving unusual reaction. Furthermore, successfully synthesized diverse series polycyclic derivatives; among quinolines, potential antitumor agents were identified using cellular vivo experiments, thereby demonstrating synthetic utility developed methodology.

Язык: Английский

---

Palladium-Catalyzed Enantioselective Isodesmic C—H Iodination

Chinese Journal of Organic Chemistry, Год журнала: 2023, Номер 43(9), С. 3325 - 3325

Опубликована: Янв. 1, 2023

Язык: Английский

---