Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2752 - 2906

Published: Aug. 10, 2021

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing plethora opportunities to synthetic organic chemists. However, performing photochemical transformation can be quite challenge because various issues related the delivery photons. These challenges barred widespread adoption steps industry. past decade, several technological innovations led more reproducible, selective, and scalable photoinduced reactions. Herein, we provide comprehensive overview these exciting advances, including flow chemistry, high-throughput experimentation, reactor design scale-up, combination photo- electro-chemistry.

Language: Английский

---

Green Carbon Science: Efficient Carbon Resource Processing, Utilization, and Recycling towards Carbon Neutrality

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 61(15)

Published: Dec. 17, 2021

Green carbon science is defined as the "study and optimization of transformation carbon-containing compounds relevant processes involved in entire cycle from resource processing, energy utilization, CO2 fixation, recycling to utilize resources efficiently minimize net emission."[1] related closely neutrality, fields have developed quickly last decade. In this Minireview, we propose concept index, recent progress petroleum refining, production liquid fuels, chemicals, materials using coal, methane, , biomass, waste plastics highlighted combination with green science. An outlook for these important provided final section.

Language: Английский

---

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(10), P. 2518 - 2531

Published: May 6, 2021

ConspectusCarbon dioxide (CO2) is not only a greenhouse gas and common waste product but also an inexpensive, readily available, renewable carbon resource. It important one-carbon (C1) building block in organic synthesis for the construction of valuable compounds. However, its utilization challenging owing to thermodynamic stability kinetic inertness. Although significant progress has been achieved, many limitations remain this field with regard substrate scope, reaction system, activation strategies.Since 2015, our group focused on CO2 synthesis. We are interested vast possibilities radical chemistry, although high reactivity radicals presents challenges controlling selectivity. hope develop highly useful transformations involving by achieving balance selectivity under mild conditions. Over past 6 years, we along other experts have disclosed radical-type carboxylative cyclizations carboxylations using CO2.We initiated research realizing Cu-catalyzed oxytrifluoromethylation allylamines heteroaryl methylamines generate 2-oxazolidones various precursors. Apart from Cu catalysis, visible-light photoredox catalysis powerful method achieve efficient cyclization. In these cases, single-electron-oxidation-promoted C–O bond formation between benzylic carbamates key step.Since carboxylic acids exist widely natural products bioactive drugs serve as bulk chemicals industry, realized further visible-light-promoted construct such chemicals. achieved selective umpolung imines, enamides, tetraalkylammonium salts, oxime esters successive single-electron-transfer (SSET) reduction. Using strategy, dearomative arylcarboxylation indoles CO2. addition incorporation 1 equiv per substrate, recently developed photoredox-catalyzed dicarboxylation alkenes, allenes, (hetero)arenes via SSET reduction, which allows two molecules into compounds diacids polymer precursors.In two-electron CO2, sought new strategies realize single-electron Inspired hypothetical electron-transfer mechanism iron–sulfur proteins, visible-light-driven thiocarboxylation alkenes catalytic iron salts promoters. The in-situ-generated Fe/S complexes likely able reduce anion, could react give stabilized radical. Moreover, charge-transfer complex (CTC) thiolate acrylate/styrene hydrocarboxylation generation or alkene anion. On basis novel CTC, organocatalytic Hantzsch ester effective reductant.

Language: Английский

---

Coupling Strategy for CO₂Valorization Integrated with Organic Synthesis by Heterogeneous Photocatalysis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(39), P. 21150 - 21172

Published: April 28, 2021

Photocatalytic reduction of CO2 to solar fuels and/or fine chemicals is a promising way increase the energy supply and reduce greenhouse gas emissions. However, conventional reaction system for photoreduction with pure H2 O or sacrificial agents usually suffers from low catalytic efficiency, poor stability, cost-ineffective atom economy. A recent surge developments, in which photocatalytic valorization integrated selective organic synthesis into one system, indicates an efficient modus operandi that enables sufficient utilization photogenerated electrons holes achieve goals sustainable economic social development. In this Review we discuss current advances cooperative photoredox systems integrate organics upgrading based on heterogeneous photocatalysis. The applications virtues strategy underlying mechanisms are discussed. ongoing challenges prospects area critically

Language: Английский

---

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

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2353 - 2428

Published: Oct. 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.

Language: Английский

---

Acridinium Salts and Cyanoarenes as Powerful Photocatalysts: Opportunities in Organic Synthesis

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(36), P. 19526 - 19549

Published: April 22, 2021

The use of organic photocatalysts has revolutionized the field photoredox catalysis, as it allows access to reactivities that were traditionally restricted transition-metal photocatalysts. This Minireview reports recent developments in acridinium ions and cyanoarene derivatives synthesis. activation inert chemical bonds well late-stage functionalization biorelevant molecules are discussed, with a special focus on their mechanistic aspects.

Language: Английский

---

Dicarboxylation of alkenes, allenes and (hetero)arenes with CO2 via visible-light photoredox catalysis

Nature Catalysis, Journal Year: 2021, Volume and Issue: 4(4), P. 304 - 311

Published: April 15, 2021

Language: Английский

---

Feeding Carbonylation with CO₂ via the Synergy of Single-Site/Nanocluster Catalysts in a Photosensitizing MOF

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(49), P. 20792 - 20801

Published: Dec. 4, 2021

Solar-driven carbonylation with CO2 replacing toxic CO as a C1 source is of considerable interest; however it remains great challenge due to the inert molecule. Herein, we integrate cobalt single-site and ultrafine CuPd nanocluster catalysts into porphyrin-based metal-organic framework construct composite photocatalysts (Cu1Pd2)z@PCN-222(Co) (z = 1.3, 2.0, 3.0 nm). Upon visible light irradiation, excited porphyrin can concurrently transfer electrons Co single sites nanoclusters, providing possibility for coupling photoreduction Suzuki/Sonogashira reactions. This multicomponent synergy in (Cu1Pd2)1.3@PCN-222(Co) not only replace dangerous gas but also dramatically promote photosynthesis benzophenone over 90% yield 97% selectivity under mild condition. Systematic investigations clearly decipher function collaboration among different components these catalysts, highlighting new insight developing sustainable protocol reactions by employing greenhouse source.

Language: Английский

---

Photocarboxylation with CO₂: an appealing and sustainable strategy for CO₂ fixation

Green Chemistry, Journal Year: 2020, Volume and Issue: 22(21), P. 7301 - 7320

Published: Jan. 1, 2020

This review discusses recent advances in the photocatalytic carboxylation of C(sp³)–X (X = H, N) bonds, C(sp²)–X N, (pseudo)halide) bonds and C(sp)–H with CO₂.

Language: Английский

---

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 364(2), P. 234 - 267

Published: Nov. 29, 2021

Abstract Fluorine‐containing moieties are widely used in the pharmaceutical, agrochemical, and material fields. Thus, these structures of immense interest fields organic synthesis medicinal chemistry. Among various fluorinated groups, difluoromethyl unit has drawn increasing attention due to its unique pharmaceutical properties. In recent years, several methods for difluoromethylated compounds have been rapidly developed. However, most treat aromatic with excess difluoromethylating reagents, which often contain organometallic compounds, so transformations generally less environmentally friendly atom‐economical. this review, we summarize development new motifs or difluoroalkenes from trifluoromethylated trifluoromethyl alkenes via single C( sp 3 )−F bond cleavage. magnified image

Language: Английский

---