Metal Stereogenicity in Asymmetric Transition Metal Catalysis

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4764 - 4794

Опубликована: Март 29, 2023

Chiral transition metal catalysts represent a powerful and economic tool for implementing stereocenters in organic synthesis, with the center providing strong chemical activation upon its interaction substrates or reagents, while overall chirality of complex achieves desired stereoselectivity. Often, chiral topology implements stereogenic center, which is then involved origin asymmetric induction. This review provides comprehensive survey reported formally constitutes stereocenter. A goes along an complex, regardless whether ligands are achiral. Implications catalyst design mechanism induction discussed half-sandwich, tetracoordinated, pentacoordinated, hexacoordinated complexes containing center. The distinguishes between originating from coordination to those solely composed optically inactive (achiral rapidly interconverting enantiomers) prior complexation (dubbed “chiral-at-metal” catalysts).

Язык: Английский

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Ligand Development for Copper-Catalyzed Enantioconvergent Radical Cross-Coupling of Racemic Alkyl Halides

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(38), С. 17319 - 17329

Опубликована: Сен. 1, 2022

The enantioconvergent cross-coupling of racemic alkyl halides represents a powerful tool for the synthesis enantioenriched molecules. In this regard, first-row transition metal catalysis provides suitable mechanism stereoconvergence by converting to prochiral radical intermediates owing their good single-electron transfer ability. contrast noble development chiral nickel catalyst, copper-catalyzed is less studied. Besides enantiocontrol issue, major challenge arises from weak reducing capability copper that slows reaction initiation. Recently, significant efforts have been dedicated basic research aimed at developing ligands halides. This perspective will discuss advances in burgeoning area with particular emphasis on strategic anionic ligand design tune initiation under thermal conditions our group.

Язык: Английский

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Light-empowered contra-thermodynamic stereochemical editing

Nature Reviews Chemistry, Год журнала: 2022, Номер 7(1), С. 35 - 50

Опубликована: Ноя. 16, 2022

Язык: Английский

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Photochemistry Journey to Multielectron and Multiproton Chemical Transformation

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(36), С. 16219 - 16231

Опубликована: Сен. 2, 2022

The odyssey of photochemistry is accompanied by the journey to manipulate "electrons" and "protons" in time, space, energy. Over past decades, single-electron (1e-) photochemical transformations have brought marvelous achievements. However, as each photon absorption typically generates only one exciton pair, it exponentially challenging accomplish multielectron proton transformations. multistep differences thermodynamics kinetics urgently require us optimize light harvesting, expedite consecutive electron transfer, interaction catalysts with substrates, coordinate transfer furnish selective bond formations. Tandem catalysis enables orchestrating different events catalytic from subpicoseconds seconds, which facilitates redox chemistries brings consecutive, value-added reactivities. Joint efforts molecular material design, mechanistic understanding, theoretical modeling will bring synthetic opportunities for fuels, fertilizers, chemicals enhanced versatility, efficiency, selectivity, scalability, thus taking better advantage photons (i.e., sunlight) our sustainable society.

Язык: Английский

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EDA photochemistry: Mechanistic investigations and future opportunities

Chem, Год журнала: 2023, Номер 9(9), С. 2390 - 2415

Опубликована: Июль 18, 2023

Язык: Английский

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Synthetic Applications of Photocatalyzed Halogen‐Radical Mediated Hydrogen Atom Transfer for C−H Bond Functionalization

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(34)

Опубликована: Май 13, 2022

Abstract The opportunity to activate C(sp 3 )−H bonds via homolytic cleavage by means of halogen radicals has long been disregarded in synthetic endeavors due the unpredictable selectivity. Nowadays, photocatalysis established itself as a method choice for generation such reactive intermediates under mild conditions. This Minireview collects recent examples showcasing how photocatalytic manifolds have used tame aggressive Hydrogen Atom Transfer (HAT) purposes. In last section this work, we address site‐selectivity issues posed methodology and show it can be guided through judicious reaction

Язык: Английский

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Enantioselective [2π + 2σ] Cycloadditions of Bicyclo[1.1.0]butanes with Vinylazaarenes through Asymmetric Photoredox Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 8372 - 8380

Опубликована: Март 18, 2024

Here we present a highly enantioselective [2π + 2σ] photocycloaddition of bicyclo[1.1.0]butanes (BCBs). The reaction uses variety vinylazaarenes as partners and is catalyzed by polycyclic aromatic hydrocarbon (PAH)-containing chiral phosphoric acid bifunctional photosensitizer. A wide array pharmaceutically important bicyclo[2.1.1]hexane (BCH) derivatives have been synthesized with high yields, enantioselectivity, diastereoselectivity. In addition to the diverse 1-ketocarbonyl-3-substituted BCBs, α/β-substituted are compatible such an unprecedented photoredox catalytic pathway, resulting in successful assembly all-carbon quaternary stereocenter or two adjacent tertiary stereocenters on product.

Язык: Английский

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Recent advances in visible light-mediated chemical transformations of enaminones

Chinese Chemical Letters, Год журнала: 2023, Номер 35(2), С. 108977 - 108977

Опубликована: Авг. 26, 2023

Язык: Английский

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Light-enabled deracemization of cyclopropanes by Al-salen photocatalysis

Nature, Год журнала: 2023, Номер 621(7980), С. 753 - 759

Опубликована: Авг. 23, 2023

Privileged chiral catalysts-those that share common structural features and are enantioselective across a range of reactions-continue to transform the chemical-research landscape1. In recent years, new reactivity modes have been achieved through excited-state catalysis, processes activated by light, but it is unclear if selectivity ground-state privileged catalysts can be matched. Although interception photogenerated intermediates cycles has partially addressed this challenge2, single, photocatalysts simultaneously regulate conspicuously scarce3. So far, precision donor-acceptor recognition motifs remain crucial in photocatalyst design4. Here we show Al-salen complexes, which well-defined photophysical properties, used for efficient photochemical deracemization5 cyclopropyl ketones (up 98:2 enantiomeric ratio (e.r.)). Irradiation at λ = 400 nm (violet light) augments commercial catalyst enable enantioselectivity regulated simultaneously. This circumvents need tailored catalyst-substrate motifs. It predicted study will stimulate re-evaluation many venerable (ground-state) processes, ultimately leading identification candidates may considered 'privileged' both models.

Язык: Английский

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Electrochemical radical-polar crossover: a radical approach to polar chemistry

Science China Chemistry, Год журнала: 2023, Номер 67(2), С. 450 - 470

Опубликована: Ноя. 3, 2023

Язык: Английский

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