Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1485 - 1542

Опубликована: Ноя. 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.

Язык: Английский

---

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

Chemical Reviews, Год журнала: 2020, Номер 121(1), С. 506 - 561

Опубликована: Май 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.

Язык: Английский

---

Visible Light-Induced Transition Metal Catalysis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1543 - 1625

Опубликована: Окт. 8, 2021

In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which led to the discovery of unprecedented transformations well improvement known reactions. this subfield complex serves double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via single catalytic cycle, thus contrasting established dual photocatalysis an exogenous photosensitizer is employed. addition, approach often synergistically combines catalyst–substrate interaction with photoinduced process, feature that uncommon conventional photoredox chemistry. This Review describes early development advances emerging field.

Язык: Английский

---

When Light Meets Nitrogen-Centered Radicals: From Reagents to Catalysts

Accounts of Chemical Research, Год журнала: 2020, Номер 53(5), С. 1066 - 1083

Опубликована: Апрель 14, 2020

ConspectusNitrogen-centered radicals (NCRs) are a versatile class of highly reactive species that have longer history than the classical carbon-based in synthetic chemistry. Depending on N-hybridization and substitution patterns, NCRs can serve as electrophiles or nucleophiles to undergo various radical transformations. Despite their power, progress nitrogen-radical chemistry is still slow compared with popularity carbon radicals, considerable potential has been largely underexplored, which is, concluded by Zard, mainly hampered "a dearth convenient access these lack awareness pertaining reactivity".Over past decade, visible-light photoredox catalysis established powerful toolbox chemists use generate diverse range intermediates from native organic functional groups via single electron transfer process energy under mild reaction conditions. This catalytic strategy typically obviates need for external stoichiometric activation reagents toxic initiators often enables traditionally inaccessible ionic chemical reactions. On basis our long-standing interest nitrogen catalysis, we emphasized tactic discover develop novel methods generating controlled fashion applications. In this Account, describe recent advances development visible-light-driven photoredox-catalyzed generation applications.Inspired natural biological proton-coupled (PCET) process, first developed oxidative deprotonation activate N–H bonds hydrazones, benzamides, sulfonamides give corresponding With species, then achieved 5-exo 6-endo cyclizations well cascade reactions regioselective manner, providing variety potentially useful heterocycles. To further expand repertoire possible NCRs, also revealed iminyl derived O-acyl cycloalkanone oxime esters, facile ring-opening C–C bond cleavage cyanoalkyl radicals. These newly formed bond-forming allow synthesis distally functionalized alkyl nitriles. Stimulated studies, wide copper-catalyzed cross-coupling Because inherent transient properties, heteroatom-centered underexplored synthesis. Building understanding fundamental time concept NCR covalent involves situ-photogenerated allyl sulfones, vinylcyclopropanes, N-tosyl vinylaziridines. thus enabled efficient difunctionalization alkenes late-stage modification complex biologically active molecules.In panoramic picture contributions since 2014 application systems field studies provide not only functionally rich molecules but some insight into exploration new reactivity modes NCRs.

Язык: Английский

---

Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds

Chemical Society Reviews, Год журнала: 2020, Номер 50(2), С. 766 - 897

Опубликована: Дек. 22, 2020

Recent developments and future prospects of visible-light photocatalysis in the late-stage functionalization pharmaceuticals natural bioactive compounds.

Язык: Английский

---

Strategies to Generate Nitrogen-centered Radicals That May Rely on Photoredox Catalysis: Development in Reaction Methodology and Applications in Organic Synthesis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 2353 - 2428

Опубликована: Окт. 8, 2021

For more than 70 years, nitrogen-centered radicals have been recognized as potent synthetic intermediates. This review is a survey designed for use by chemists engaged in target-oriented synthesis. summarizes the recent paradigm shift access to and application of N-centered enabled visible-light photocatalysis. broadens streamlines approaches many small molecules because photocatalysis conditions are mild. Explicit attention paid innovative advances N–X bonds radical precursors, where X = Cl, N, S, O, H. clarity, key mechanistic data noted, available. Synthetic applications limitations summarized illuminate tremendous utility photocatalytically generated radicals.

Язык: Английский

---

Cleavage of Carbon–Carbon σ-Bonds of Four-Membered Rings

Chemical Reviews, Год журнала: 2020, Номер 121(1), С. 264 - 299

Опубликована: Сен. 23, 2020

This article reviews synthetic transformations involving cleavage of a carbon-carbon bond four-membered ring, with particular focus on the examples reported during period from 2011 to end 2019. Most significant is progress catalytic reactions oxidative addition bonds onto transition metals or β-carbon elimination metal alkoxides. When they are looked at perspectives, offer unique and efficient methods build complex natural products structures that difficult construct by conventional methods. On other hand, β-scission radical intermediates has also attracted increasing attention as an alternative elementary step cleave bonds. Its site-selectivity often complementary metal-catalyzed reactions. In addition, Lewis acid-mediated thermally induced ring-opening cyclobutanone derivatives garnered renewed attention. whole, these demonstrate potentials structurally strained ring compounds for construction organic skeletons.

Язык: Английский

---

Multicomponent reactions and photo/electrochemistry join forces: atom economy meets energy efficiency

Chemical Society Reviews, Год журнала: 2022, Номер 51(6), С. 2313 - 2382

Опубликована: Янв. 1, 2022

Visible-light photoredox catalysis has been regarded as an extremely powerful tool in organic chemistry, bringing the spotlight back to radical processes. The versatility of photocatalyzed reactions already demonstrated be effective providing alternative routes for cross-coupling well multicomponent reactions. photocatalyst allows generation high-energy intermediates through light irradiation rather than using highly reactive reagents or harsh reaction conditions. In a similar vein, electrochemistry experienced fruitful renaissance generating without need any catalyst. Such milder approaches pose basis toward higher selectivity and broader applicability. electrochemical reactions, species acts starter cascade events. This diverse reactivity use is usually not covered by classical methods. Owing availability cheaper more standardized photo- reactors, easily scalable flow-setups, it surprising that these two fields have become areas increased research interest. Keeping view, this review aimed at overview synthetic design MCRs involving and/or activation crucial step with particular focus on choice difunctionalized reagent.

Язык: Английский

---

Copper-photocatalyzed ATRA reactions: concepts, applications, and opportunities

Chemical Society Reviews, Год журнала: 2022, Номер 51(13), С. 5287 - 5299

Опубликована: Янв. 1, 2022

This review summarizes the different applications and underlying concepts that are applied for Cu( i )- or ii )-photocatalyzed difunctionalizations of alkenes.

Язык: Английский

---

Reactivity of oximes for diverse methodologies and synthetic applications

Nature Synthesis, Год журнала: 2022, Номер 1(1), С. 24 - 36

Опубликована: Янв. 12, 2022

Язык: Английский

---