Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1485 - 1542

Published: Nov. 18, 2021

The merger of photoredox catalysis with transition metal catalysis, termed metallaphotoredox has become a mainstay in synthetic methodology over the past decade. Metallaphotoredox combined unparalleled capacity for bond formation broad utility photoinduced electron- and energy-transfer processes. Photocatalytic substrate activation allowed engagement simple starting materials metal-mediated bond-forming Moreover, electron or energy transfer directly key organometallic intermediates provided novel modes entirely complementary to traditional catalytic platforms. This Review details contextualizes advancements molecule construction brought forth by metallaphotocatalysis.

Language: Английский

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Visible Light-Driven Radical-Mediated C–C Bond Cleavage/Functionalization in Organic Synthesis

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(1), P. 506 - 561

Published: May 29, 2020

Thermal C–C bond cleavage reactions allow the construction of structurally diverse molecular skeletons via predictable and efficient reorganizations. Visible light photoredox-catalyzed radical-mediated have recently emerged as a powerful alternative method for overcoming thermodynamic kinetic barrier in scaffolds. In recent years, plethora elegant useful been invented, products are sometimes otherwise inaccessible by classic thermal reactions. Considering great influence synthetic potential these reactions, we provide summary state art visible light-driven cleavage/functionalization strategies with specific emphasis on working models. We hoped that this review will be medicinal organic chemists inspire further reaction development interesting area.

Language: Английский

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Cooperative Coupling of Oxidative Organic Synthesis and Hydrogen Production over Semiconductor-Based Photocatalysts

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13051 - 13085

Published: Aug. 11, 2021

Merging hydrogen (H2) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H2 fuel and high-value chemicals can be coproduced under mild conditions using light as sole energy input. Following this dual-functional photocatalytic strategy, dreamlike pathway for constructing C–C/C–X (X = C, N, O, S) bonds from abundant readily available X–H bond-containing compounds concomitant release of fulfilled without need external chemical reagents, thus offering green fascinating synthetic strategy. In review, we begin by presenting concise overview on general background traditional production then focus fundamental principles cooperative coupling selective simultaneous utilization photoexcited electrons holes over semiconductor-based catalysts to meet economic sustainability goal. Thereafter, put dedicated emphasis recent key progress various transformations, including alcohol oxidation, methane conversion, amines coupling, cross-coupling, cyclic alkanes dehydrogenation, reforming lignocellulosic biomass, so on. Finally, remaining challenges future perspectives flourishing area have been critically discussed. It anticipated that review will provide enlightening guidance rational design such system, thereby stimulating development economical environmentally benign solar generation value-added fine chemicals.

Language: Английский

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The Persistent Radical Effect in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(1), P. 74 - 108

Published: May 22, 2019

Abstract Radical–radical couplings are mostly nearly diffusion‐controlled processes. Therefore, the selective cross‐coupling of two different radicals is challenging and not a synthetically valuable transformation. However, if have lifetimes they generated at equal rates, will become dominant process. This high cross‐selectivity based on kinetic phenomenon called persistent radical effect (PRE). In this Review, an explanation PRE supported by simulations simple model systems provided. Radical stabilities discussed within context their lifetimes, various examples PRE‐mediated radical–radical in synthesis summarized. It shown that restricted to coupling with transient radical. If one partner longer‐lived than other radical, operates achieved. important point expands scope chemistry. The Review divided into parts, namely 1) or organic 2) “radical–metal crossover reactions”; here, metal‐centered species more generally transition‐metal complexes able react discussed—a field has flourished recently.

Language: Английский

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Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(8), P. 4373 - 4505

Published: March 19, 2021

This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution decarboxylative oxidative substitutions. For each reaction, catalytic data, as well examples of their application to synthesis complex molecules, are collected. Sections which we discuss key aspects for high selectivity a comparison with other metals (with advantages disadvantages) also included. asymmetric substitution, data grouped according type nucleophile employed. Because prominent position use stabilized carbon nucleophiles heteronucleophiles, many chiral ligands have been developed. To better compare results, they presented by ligand types. reactions mainly promoted PHOX or Trost ligands, justifies organizing this section chronological order. results used.

Language: Английский

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Recent advances in photoredox and nickel dual-catalyzed cascade reactions: pushing the boundaries of complexity

Chemical Science, Journal Year: 2020, Volume and Issue: 11(16), P. 4051 - 4064

Published: Jan. 1, 2020

Cascade reactions that produce multiple chemical bonds in one synthetic operation are important the efficient construction of complex molecules.

Language: Английский

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Hantzsch esters: an emerging versatile class of reagents in photoredox catalyzed organic synthesis

Organic & Biomolecular Chemistry, Journal Year: 2019, Volume and Issue: 17(29), P. 6936 - 6951

Published: Jan. 1, 2019

This minireview highlights the recent advances in chemistry of Hantzsch esters photoredox catalyzed organic synthesis, with particular emphasis placed on reaction mechanisms.

Language: Английский

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Nickel/Photo-Cocatalyzed Asymmetric Acyl-Carbamoylation of Alkenes

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(5), P. 2180 - 2186

Published: Jan. 23, 2020

An unprecedented asymmetric acyl-carbamoylation of pendant alkenes tethered on aryl carbamic chlorides with both aliphatic and aromatic aldehydes has been developed via the cooperative catalysis a chiral nickel-PHOX complex tetrabutylammonium decatungstate. This reaction represents first example merging hydrogen-atom-transfer photochemistry transition metal in difunctionalization alkenes. Using this protocol, variety oxindoles bearing challenging quaternary stereogenic center are furnished under mild conditions highly enantioselective manner.

Language: Английский

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Asymmetric Propargylic Radical Cyanation Enabled by Dual Organophotoredox and Copper Catalysis

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(15), P. 6167 - 6172

Published: March 31, 2019

The first asymmetric propargylic radical cyanation was realized through a dual photoredox and copper catalysis. An organic photocatalyst serves to both generate propargyl radicals oxidize Cu(I) species Cu(II) species. A chiral Cu complex functions as an efficient organometallic catalyst resemble the cyanide in enantio-controlled manner. Thus, diverse range of optically active cyanides were produced with high reaction efficiency enantioselectivities (28 examples, 57–97% yields 83–98% ee). Moreover, mechanistic investigations including experiments density functional theory calculations performed illustrate on pathway stereochemical results.

Language: Английский

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Transition metal-catalysed allylic functionalization reactions involving radicals

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(17), P. 6186 - 6197

Published: Jan. 1, 2020

In this tutorial review, different types of transition metal-catalysed allylic functionalization reactions involving radicals are highlighted.

Language: Английский

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