Electron Donor‐Acceptor (EDA) Complex Enabled C−C Cross‐Coupling Reactions of α‐Amino Radicals

Asian Journal of Organic Chemistry, Год журнала: 2024, Номер 13(6)

Опубликована: Апрель 18, 2024

Abstract Electron‐donor acceptor (EDA) complex has been an integral part of visible‐light photocatalysis and is different from the traditional photoredox catalysis, which requires exogenous photocatalyst, typically a colored compound to initiate photocatalytic cycle. Interestingly, EDA‐complex photochemistry found profound use in activating inert α‐C−H bonds amines. The strategy relied upon formation between donor (amine) (Lewis acid), harvesting light energy perform SET process generate radical cation anion intermediates. then loses activated acidic proton (because SET, acidity α‐proton increases by lowering BDE) form α‐amino radical, participates various C−C coupling cascades. In this review, conceptual approaches for generation radicals their bond‐forming reaction under triggered will be discussed with particular emphasis on mechanism 2018 onwards.

Язык: Английский

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Enantioselective Giese Additions of Prochiral α-Amino Radicals

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(49), С. 22451 - 22457

Опубликована: Дек. 1, 2022

Amines featuring an adjacent stereocenter are important building blocks, and recent years have seen remarkable growth in methods forming these via prochiral α-amino radical intermediates. However, very few can exert control over the newly formed stereocenter. We disclose a strategy to overcome this context of one most widely used carbon–carbon bond reactions, Giese reaction. Incorporation removable basic heteroarene into substrate enables network attractive noncovalent interactions between phosphoric acid catalyst, subsequently radical, acceptor, allowing catalyst during C–C step. Deprotection products leads analogues γ-aminobutyric acid. anticipate that will be applicable other asymmetric transformations which is presently challenging.

Язык: Английский

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Dual Catalysis of Gold Nanoclusters: Photocatalytic Cross‐Dehydrogenative Coupling by Cooperation of Superatomic Core and Molecularly Modified Staples**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(2)

Опубликована: Ноя. 6, 2023

Abstract Thiolate‐protected gold nanoclusters (AuNCs) have attracted significant attention as nano‐catalysts, revealing a superatomic core and gold‐thiolate staples distinct structural units. Here, we demonstrate the unprecedented dual catalytic activity of thiolate‐protected [Au 25 (SR) 18 ] − nanoclusters, involving both photosensitized 1 O 2 generation by Au 13 carbon‐carbon bond formation facilitated 3 staples. This synergistic combination two different units enables efficient cross‐dehydrogenative coupling terminal alkynes tertiary aliphatic amines to afford propargylamines in high yields up 93 %. Mixed‐ligand AuNCs bearing thiolate alkynyl ligands revealed intermediacy alkynyl‐exchanged toward photosensitization C−C bond‐forming cycles. Density functional theory calculations also supported AuNCs. Thus, use ligand‐protected metal has enabled development an exceptional multifunctional catalyst, wherein nanocluster components facilitate cooperative photo‐ chemo‐catalysis.

Язык: Английский

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Deconstructive Carboxylation of Activated Alkenes with Carbon Dioxide

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(5)

Опубликована: Дек. 11, 2023

Carboxylation with carbon dioxide (CO

Язык: Английский

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Dimerizing cascades of enallenamides reveal the visible-light-promoted activation of cumulated C–C double bonds

Chemical Science, Год журнала: 2022, Номер 13(9), С. 2632 - 2639

Опубликована: Янв. 1, 2022

Visible-light promoted activation of allenamides allowed us to disclose original dimerizing cascades that provide highly elaborate molecular architectures in a concise and mild fashion.

Язык: Английский

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