Ligand‐to‐Metal Charge Transfer (LMCT) Photochemistry at 3d‐Metal Complexes: An Emerging Tool for Sustainable Organic Synthesis

ChemCatChem, Год журнала: 2022, Номер 14(19)

Опубликована: Авг. 11, 2022

Abstract Despite the rich photochemistry of 3d‐metal complexes, utilization excited‐state reactivity these compounds in organic synthesis has been historically overlooked. The advent photoredox catalysis changed perception synthetic chemists towards photochemistry, and nowadays potential photoinduced, outer‐sphere single‐electron transfer events is widely recognized. More recently, an emerging new mode photoactivation taken spotlight, based on inner‐sphere triggered by population ligand‐to‐metal charge‐transfer (LMCT) excited states. Contrarily to photoredox, LMCT‐activation does not rely matching redox potentials, offers unique profiles particularly well suited Earth‐abundant metal complexes. Those appealing features are propelling development methods using this blueprint generate highly reactive open‐shell species under mild conditions. aim contribution provide a didactical tool for comprehension concept facilitate methodologies achieve sustainable chemical transformations.

Язык: Английский

---

Photoactive Copper Complexes: Properties and Applications

Chemical Reviews, Год журнала: 2022, Номер 122(22), С. 16365 - 16609

Опубликована: Ноя. 9, 2022

Photocatalyzed and photosensitized chemical processes have seen growing interest recently become among the most active areas of research, notably due to their applications in fields such as medicine, synthesis, material science or environmental chemistry. Among all homogeneous catalytic systems reported date, photoactive copper(I) complexes been shown be especially attractive, not only alternative noble metal complexes, extensively studied utilized recently. They are at core this review article which is divided into two main sections. The first one focuses on an exhaustive comprehensive overview structural, photophysical electrochemical properties mononuclear typical examples highlighting critical structural parameters impact being presented enlighten future design complexes. second section devoted application (photoredox catalysis organic reactions polymerization, hydrogen production, photoreduction carbon dioxide dye-sensitized solar cells), illustrating progression from early current state-of-the-art showcasing how some limitations can overcome with high versatility.

Язык: Английский

---

Carboxylic Acids as Adaptive Functional Groups in Metallaphotoredox Catalysis

Accounts of Chemical Research, Год журнала: 2022, Номер 55(23), С. 3481 - 3494

Опубликована: Ноя. 22, 2022

The development of palladium-catalyzed cross-coupling methods for the activation C(sp2)-Br bonds facilitated access to arene-rich molecules, enabling a concomitant increase in prevalence this structural motif drug molecules recent decades. Today, there is growing appreciation value incorporating saturated C(sp3)-rich scaffolds into pharmaceutically active as means achieve improved solubility and physiological stability, providing impetus develop new coupling strategies these challenging motifs most straightforward way possible. As an alternative classical two-electron chemistry, redox chemistry can enable elusive transformations, recently, by interfacing abundant first-row transition-metal catalysis with photoredox catalysis. such, functionalization ubiquitous versatile functional handles such (aliphatic) carboxylic acids via metallaphotoredox has emerged valuable field research over past eight years.In Account, we will outline progress methodologies that employ aliphatic (hetero)aromatic adaptive groups. Whereas decarboxylative often necessitate preactivated form redox-active esters or ligands hypervalent iodine reagents, direct use native acid functionality are highly desired have been accomplished through protocols. found bench-stable undergo diverse alkylation, arylation, amination, trifluoromethylation, leveraging prevalent transition metals nickel copper. Likewise, aryl now able halogenation borylation, entry points traditional, primarily palladium- copper-catalyzed strategies. Given breadth group tolerance employed reaction conditions, late-stage toward targets become standard tool design, synthesis various diversified molecules. rapid rise positively inspired pharmaceutical discovery be further accelerated novel development. achievement generality optimization campaigns allows future breakthroughs render protocols more reliable applicable industry. This article intended highlight, particular, (i) employment (hetero)aryl powerful (ii) need still-elusive selective transformations.We strongly believe functionalities inspire researchers across world investigate complex molecular targets.

Язык: Английский

---

Photocatalytic hydrofluoroalkylation of alkenes with carboxylic acids

Nature Chemistry, Год журнала: 2023, Номер 15(12), С. 1683 - 1692

Опубликована: Ноя. 13, 2023

Язык: Английский

---

Metal-Free Amino(hetero)arylation and Aminosulfonylation of Alkenes Enabled by Photoinduced Energy Transfer

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(30), С. 16630 - 16641

Опубликована: Июль 24, 2023

β-(Hetero)arylethylamines are privileged structural motifs found in many high-value organic molecules, including pharmaceuticals and natural products. To construct these important molecular skeletons, previous methods mainly achieved by amino(hetero)arylation reaction with the aid of transition metals preactivated substrates. Herein, we report a metal-free photoinduced intermolecular for single-step installation both (hetero)aryl iminyl groups across alkenes an efficient regioselective manner. This method shows broad scope (up to 124 examples) excellent tolerance various olefins─from simplest ethylene complex multisubstituted can all participate reaction. Furthermore, aminosulfonylation be also conducted presence sodium bisulfite as SO2 source.

Язык: Английский

---

Synthetic Application of Bismuth LMCT Photocatalysis in Radical Coupling Reactions

ACS Catalysis, Год журнала: 2023, Номер 13(2), С. 1125 - 1132

Опубликована: Янв. 9, 2023

Ligand-to-metal charge transfer (LMCT) photocatalysis allows the activation and synthetic utilization of halides other heteroatoms in metal complexes. Many metals are known to undergo LMCT but so far remain underutilized field catalysis. A screening assay identifying activity helped us expand this catalysis concept application bismuth organic radical coupling reactions. We demonstrate its for generation two different radicals (chlorine carboxyl) net-oxidative as well redox-neutral photochemical Detailed investigation model Giese-type revealed BiCl4– BiCl52– catalytically active species under 385 nm irradiation. Combined cyclic voltammetry UV–vis studies gave insight into reactivity highly reactive bismuth(II) catalyst fragment.

Язык: Английский

---

Free Carboxylic Acids: The Trend of Radical Decarboxylative Functionalization

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(21)

Опубликована: Апрель 7, 2023

Abstract The exceptional versatility of carboxylic acids has been extensively exploited in organic synthesis across several decades. There a recent upsurge radical decarboxylative transformations. process can be initiated under mild conditions, and the resultant radicals have orthogonal reactivities to closed‐shell species, thus providing immense opportunities for streamlining novel reactions. use free is most desirable owing its high atom step economy. Aiming demonstrate attractiveness strategy inspire chemists tackle existing challenges, this review outlines advances on functionalization acids.

Язык: Английский

---

Direct Decarboxylation of Trifluoroacetates Enabled by Iron Photocatalysis**

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

Опубликована: Дек. 13, 2023

Trifluoroacetates are the most abundant and accessible sources of trifluoromethyl groups, which key components in pharmaceuticals agrochemicals. The generation reactive radicals from trifluoroacetates requires their decarboxylation, is hampered by high oxidation potential. This constitutes a major challenge for redox-based methods, because need to pair redox potentials with trifluoroacetate. Here we report strategy based on iron photocatalysis promote direct photodecarboxylation that displays reactivity features escape limitations. Our synthetic design has enabled use trifluoromethylation more easily oxidizable organic substrates, offering new opportunities late-stage derivatization campaigns using chemical feedstocks, Earth-abundant catalysts, visible-light.

Язык: Английский

---

Photochemical iron-catalyzed decarboxylative azidation via the merger of ligand-to-metal charge transfer and radical ligand transfer catalysis

Chem Catalysis, Год журнала: 2023, Номер 3(6), С. 100603 - 100603

Опубликована: Апрель 12, 2023

Язык: Английский

---

Visible-Light-Induced Decarboxylative Fluorination of Aliphatic Carboxylic Acids Catalyzed by Iron

Organic Letters, Год журнала: 2022, Номер 24(32), С. 5972 - 5976

Опубликована: Авг. 11, 2022

An efficient and inexpensive protocol for the direct decarboxylative fluorination of aliphatic carboxylic acids catalyzed with iron salts under visible light is presented. This new method allows facile a diverse array even on gram scale using Schlenk flask without loss efficiency. Mechanistic studies suggest that photoinduced ligand-to-metal charge transfer process enables generation key step to generate carboxyl radical intermediates.

Язык: Английский

---