Visible Light-Induced Reactions of Diazo Compounds and Their Precursors

Chemical Reviews, Год журнала: 2024, Номер 124(11), С. 7214 - 7261

Опубликована: Май 16, 2024

In recent years, visible light-induced reactions of diazo compounds have attracted increasing attention in organic synthesis, leading to improvement existing reactions, as well the discovery unprecedented transformations. Thus, photochemical or photocatalytic generation both carbenes and radicals provide milder tools toward these key intermediates for many valuable However, vast majority transformations represent new reactivity modes compounds, which are achieved by decomposition photoredox catalysis. particular, use a redox-active photocatalysts opens avenue plethora radical reactions. The application methods led inaccessible classical associated with metal carbenes. most cases, act sources but can also serve acceptors. Importantly, described processes operate under mild, practical conditions. This Review describes this subfield compound chemistry, particularly focusing on advancements.

Язык: Английский

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Visible-Light-Induced [4 + 3]-Annulation of Carbonyl Ylides with Alkenyl Pyrazolinone for Constructing [4.2.1]-Oxo-Bridged Oxocine Skeleton

Organic Letters, Год журнала: 2025, Номер 27(2), С. 709 - 714

Опубликована: Янв. 7, 2025

Herein, we present a visible-light-induced protocol for the synthesis of highly functionalized oxo-bridged oxocine skeletons. This method generates carbenes via ortho-acyl diazo compounds, which are rapidly intercepted by oxygen atom an intermolecular acyl group to form cyclic 1,3-dipole. The in situ generated reactive 1,3-dipole undergoes facile formal [4 + 3] cycloaddition with alkenyl pyrazolinone, yielding [4.2.1]-oxo-bridged compounds.

Язык: Английский

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A Spiro Phosphamide Catalyzed Enantioselective Proton Transfer of Ylides in a Free Carbene Insertion into N−H Bonds

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Фев. 14, 2023

Free carbene readily causes multiple side reactions due to its high energy, thus asymmetric transformation is very difficult. We present here our findings of high-pKa Brønsted acid catalysts that enable free insertion into N-H bonds amines prepare chiral α-amino derivatives with enantioselectivity. Under irradiation visible light, diazo compounds produce high-energy carbenes are captured by form ylide intermediates, and then the newly designed acids, spiro phosphamides, promote proton transfer ylides afford products. Computational kinetic studies uncover principle for rational design proton-transfer explain how accelerate this provide stereocontrol.

Язык: Английский

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A visible-light-promoted metal-free approach for N–H insertions by using donor/donor diazo precursors

Green Chemistry, Год журнала: 2024, Номер 26(8), С. 4600 - 4608

Опубликована: Янв. 1, 2024

A metal-free and catalyst-free strategy is reported to achieve N–H insertions by coupling N -tosylhydrazones with diverse amines including aminopyridines, anilines, aliphatic amines, other nucleophiles such as imidazoles indoles.

Язык: Английский

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Visible photons as ideal reagents for the activation of coloured organic compounds

Chemical Society Reviews, Год журнала: 2024, Номер 53(10), С. 4926 - 4975

Опубликована: Янв. 1, 2024

In search for the perfect wave(length). This review is dedicated to recent efforts in development of visible light driven photochemical strategies occurring coloured organic compounds.

Язык: Английский

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Enantioselective organocatalytic strategies to access noncanonical α-amino acids

Chemical Science, Год журнала: 2024, Номер 15(16), С. 5832 - 5868

Опубликована: Янв. 1, 2024

Organocatalytic asymmetric synthesis has evolved over the years and continues to attract interest of many researchers worldwide. Enantiopure noncanonical amino acids (ncAAs) are valuable building blocks in organic synthesis, medicinal chemistry, chemical biology. They employed elaboration peptides proteins with enhanced activities and/or improved properties compared their natural counterparts, as chiral catalysts, ligand design, for syntheses complex molecules, including products. The linkage ncAA enantioselective organocatalysis, subject this perspective, tries imitate biosynthetic process. Herein, we present contemporary earlier developments field organocatalytic activation simple feedstock materials, providing potential ncAAs diverse side chains, unique three-dimensional structures, a high degree functionality. These strategies, useful forging wide range C-C, C-H, C-N bonds combinations thereof, vary from classical name reactions, such Ugi, Strecker, Mannich most advanced concepts deracemisation, transamination, carbene N-H insertion. Concurrently, some interesting mechanistic studies/models, information on chirality transfer Finally, perspective highlights, through diversity (AAs) not selected by nature protein incorporation, generic modes activation, induction, reactivity commonly used, enamine, hydrogen bonding, Brønsted acids/bases, phase-transfer reflecting increasingly important role applied chemistry.

Язык: Английский

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Carbene Formation or Reduction of the Diazo Functional Group? An Unexpected Solvent‐Dependent Reactivity of Cyclic Diazo Imides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Июль 28, 2023

The control of the reactivity diazo compounds is commonly achieved by choice a suitable catalyst, e.g. via stabilization singlet carbenes or radical intermediates. Herein, we report on light-promoted cyclic imides with thiols, where solvent results in two fundamentally different reaction pathways. In dichloromethane (DCM), carbene formed initially and engages cascade C-H functionalization/thiolation to deliver indane-fused pyrrolidines good excellent yields. When switching acetonitrile solvent, pathway shut down an unusual reduction compound occurs under otherwise identical conditions, aryl thiol acts as reductant. A combined set experimental computational studies was carried out obtain mechanistic understanding support that indane formation proceeds insertion triplet carbene, while electron transfer process.

Язык: Английский

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Photochemical multicomponent transformation of acceptor-only diazoalkanes by merging their cycloaddition and carbene reactivities

Chinese Chemical Letters, Год журнала: 2023, Номер 34(9), С. 108335 - 108335

Опубликована: Март 15, 2023

Язык: Английский

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How achiral Brønsted acid is involved in co-catalyst model with chiral phosphoric acid for construction of quaternary carbon stereocenter

Chem Catalysis, Год журнала: 2024, Номер 4(3), С. 100918 - 100918

Опубликована: Фев. 7, 2024

Язык: Английский

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Carbene-induced ring-opening reactions of five-/six-membered cyclic ethers: expanding the frontiers of functional group introduction and molecular architecture construction

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The multi-component ring-opening reactions of cyclic ethers offer an efficient strategy for the rapid introduction multiple functional groups and construction complex molecular architectures.

Язык: Английский

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