Biomimetic Catalytic Remote Desaturation of Aliphatic Alcohols DOI Creative Commons
Kaiming Zuo,

Jing Zhu,

Faral Akhtar

и другие.

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 23, 2024

Herein we present photoinduced cobaloxime-catalyzed selective remote desaturation of aliphatic alcohols. This transformation, which proceeds efficiently at room temperature, facilitates the synthesis valuable cyclic and acyclic allylic homoallylic alcohols from readily available saturated Remarkably, this method obviates need for external oxidants, noble metal catalysts, phosphine ligands.

Язык: Английский

Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play DOI Creative Commons
Fabio Juliá

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4665 - 4680

Опубликована: Март 5, 2025

Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected many decades by careful selection of centers ligands, giving rise to synthetic methods with unparalleled efficiency chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful dramatically alter the outcome catalytic reactions, providing access innovative pathways remarkable potential. In this context, adoption photochemical conditions mainstream strategy drive reactions unveiled exciting opportunities exploit rich excited-state framework transition metals applications. This Perspective examines advances in application complexes standalone photocatalysts, exploiting innate reactivity their excited states beyond common use photoredox catalysts. An account relevant examples dissected provide discussion on electronic reorganization, orbitals involved, associated different types states. analysis aims practitioners fundamental principles guiding strategies understand, design, apply light-activation homogeneous synthesis.

Язык: Английский

Процитировано

4

Aryl-to-alkyl radical relay Heck reaction of amides with vinyl arenes DOI Creative Commons

Yu-jia Du,

Xia-xin Sheng,

Junhua Li

и другие.

Chemical Science, Год журнала: 2023, Номер 14(13), С. 3580 - 3586

Опубликована: Янв. 1, 2023

Herein, a photo-induced palladium catalyzed aryl-to-alkyl radical relay Heck reaction at α-C(sp 3 )–H site of amide has been developed. This method is scalable and operationally simple. Mechanistic studies reveal the nature this transformation.

Язык: Английский

Процитировано

31

Biomimetic Photoexcited Cobaloxime Catalysis in Organic Synthesis DOI Creative Commons
Phong Dam, Kaiming Zuo, Luis Miguel Azofra

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(33)

Опубликована: Май 22, 2024

Abstract Drawing inspiration from nature has long been a cornerstone of chemical innovation, with natural systems offering wealth untapped potential for discovery. In this minireview, we delve into the burgeoning field cobaloxime catalysis in organic synthesis, which mimics catalytic activity organometallic alkylcobalamine enzymes. Our focus lies on elucidating latest advancements area, as well delineating primary mechanistic pathways at play. By describing, and comparing these mechanisms, provide comprehensive overview current state‐of‐the‐art, while also shedding light key unresolved challenges that await further exploration.

Язык: Английский

Процитировано

13

Photocatalyzed H2-Acceptorless Dehydrogenative Borylation by Using Amine Borane DOI
Haowen Jiang,

Wan‐Lei Yu,

Dong Wang

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(11), С. 8666 - 8675

Опубликована: Май 20, 2024

Catalytic dehydrogenative borylation of alkenes is arguably the most straightforward approach for synthesizing alkenyl boronates, as it eliminates need alkene or boranes prefunctionalizion. While transition-metal catalysis has conventionally been employed this transformation, competitive side reactions including hydroborylation, overborylation, and regioisomer formation always exist. In study, we present a radical catalytic borylation, which involves synergistic merger photoredox/HAT/cobalt catalysis, thereby circumventing necessity noble metals, sacrificial hydrogen acceptors, high temperatures. This method employs stable cost-effective amine borane reagents feedstocks, resulting in sole byproduct H2. methodology facilitates conversion diverse array functionalized into valuable organoboron reagents. Furthermore, late-stage complex molecules demonstrates levels site selectivity.

Язык: Английский

Процитировано

12

Decatungstate/Cobalt Dual Catalyzed Dehydrogenation of Ketones Enabled by Polarity-Matched Site-Selective Activation DOI
Bin Sun, Jia‐Yin Wang,

Shuangshuang Zhou

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(14), С. 11138 - 11146

Опубликована: Июль 11, 2024

Язык: Английский

Процитировано

12

Selective N-α-C–H alkylation of cyclic tertiary amides via visible-light-mediated 1,5-hydrogen atom transfer DOI
Junlei Wang,

Qinglin Xie,

Guocheng Gao

и другие.

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(17), С. 4394 - 4399

Опубликована: Янв. 1, 2023

Herein, we report an effective C–H bond activation-alkylation strategy for 2-iodobenzoyl protected cyclic amines at the N -α-position through a visible-light mediated 1,5-hydrogen atom transfer (HAT) process.

Язык: Английский

Процитировано

19

Direct C(sp3)-H functionalization with aryl and alkyl radicals as intermolecular hydrogen atom transfer (HAT) agents DOI
Jia‐Lin Tu, Binbin Huang

Chemical Communications, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Recent years have witnessed the emergence of direct intermolecular C(sp

Язык: Английский

Процитировано

9

Cooperative Fe/Co-Catalyzed Remote Desaturation for the Synthesis of Unsaturated Amide Derivatives DOI
Yanjun Wan, Emmanuel Ramírez,

Ayzia Ford

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(7), С. 4985 - 4992

Опубликована: Фев. 6, 2024

Unsaturated amides represent common functional groups found in natural products and bioactive molecules serve as versatile synthetic building blocks. Here, we report an iron(II)/cobalt(II) dual catalytic system for the syntheses of distally unsaturated amide derivatives. The transformation proceeds through iron nitrenoid-mediated 1,5-hydrogen atom transfer (1,5-HAT) mechanism. Subsequently, radical intermediate undergoes hydrogen abstraction from vicinal methylene by a cobaloxime catalyst, efficiently yielding β,γ- or γ,δ-unsaturated derivatives under mild conditions. efficiency Co-mediated HAT can be tuned varying different auxiliaries, highlighting generality this protocol. Remarkably, desaturation protocol is also amenable to practical scalability, enabling synthesis carbamates ureas, which readily converted into various valuable molecules.

Язык: Английский

Процитировано

7

Accessing Benzoazepine Derivatives via Photoinduced Radical Relay Formal [5 + 2] Reaction of Amide/Alkyne Enabled by Palladium Catalysis DOI

Yu-jia Du,

Xia-xin Sheng,

Luning Tang

и другие.

Organic Letters, Год журнала: 2024, Номер 26(13), С. 2662 - 2667

Опубликована: Март 26, 2024

A novel class of alkyne-tethered amides facilitates an unprecedented photoinduced palladium-catalyzed radical relay formal [5 + 2] reaction. This innovative strategy allows for the rapid construction diverse fused benzoazepine structures, yielding structurally and compelling compounds. With a broad substrate scope excellent functional group tolerance, methodology synthesizes biologically active Notably, resulting tricyclic benzo[b]azepines offer diversification opportunities through simple transformations. DFT calculations elucidate seven-membered ring closure mechanism involving alkenyl Pd(I) rebound alongside concerted metalation–deprotonation (CMD) process.

Язык: Английский

Процитировано

5

Transition-Metal-Catalyzed Remote C–H Bond Functionalization of Cyclic Amines DOI Creative Commons
Weijie Chen, Xiaoyu Yang, Xi Cao

и другие.

SynOpen, Год журнала: 2022, Номер 06(04), С. 286 - 305

Опубликована: Авг. 24, 2022

Abstract C–H bond functionalization is one of the most effective strategies for rapid synthesis cyclic amines containing substituents on ring, which are core structures many bioactive molecules. However, it much more challenging to perform this strategy remote bonds compared α-C–H amines. This graphical review aims provide a concise overview transition-metal-catalyzed methods Examples categorized and demonstrated according mechanistic pathways that initiate reactions amine substrates. Where relevant, selected substrate scope detailed reaction mechanisms given.

Язык: Английский

Процитировано

19