Chemical Communications, Journal Year: 2024, Volume and Issue: 60(44), P. 5735 - 5738
Published: Jan. 1, 2024
Electroreductive ring-opening carboxylation of styrene carbonates with carbon dioxide to achieve dicarboxylic acids and/or β -hydroxy has been developed via the selective cleavage C(sp 3 )–O bond in cyclic carbonates.
Language: Английский
Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11269 - 11335
Published: Sept. 26, 2023
Late-stage functionalization (LSF) constitutes a powerful strategy for the assembly or diversification of novel molecular entities with improved physicochemical biological activities. LSF can thus greatly accelerate development medicinally relevant compounds, crop protecting agents, and functional materials. Electrochemical synthesis has emerged as an environmentally friendly platform transformation organic compounds. Over past decade, electrochemical late-stage (eLSF) gained major momentum, which is summarized herein up to February 2023.
Language: Английский
Citations
148
Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 6078 - 6144
Published: April 17, 2024
Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed
Language: Английский
Citations
39
Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(4)
Published: Oct. 24, 2022
Alcohols and their derivatives are ubiquitous versatile motifs in organic synthesis. Deoxygenative transformations of these compounds often challenging due to the thermodynamic penalty associated with cleavage C-O bond. However, electrochemically driven redox events have been shown facilitate bond alcohols either through direct electron transfer or use mediators electroactive catalysts. Herein, a comprehensive overview preparative mediated protocols for activation functionalization is detailed, including indirect electrosynthetic methods, as well photoelectrochemical strategies.
Language: Английский
Citations
55
Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(1), P. 263 - 316
Published: Dec. 7, 2023
The employment of light and/or electricity - alternatively to conventional thermal energy unlocks new reactivity paradigms as tools for chemical substrate activations. This leads the development synthetic reactions and a vast expansion spaces. review summarizes recent developments in photo- electrochemical activation strategies functionalization strong bonds particularly carbon-heteroatom (C-X)
Language: Английский
Citations
43
Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104
Published: Dec. 1, 2023
After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.
Language: Английский
Citations
41
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(31), P. 16966 - 16972
Published: July 27, 2023
We present a new, unified approach for the transformation of benzylic and allylic alcohols, aldehydes, ketones into boronic esters under electroreductive conditions. Key to our strategy is use readily available pinacolborane, which serves both as an activator electrophile by first generating redox-active trialkylborate species then delivering desired deoxygenatively borylated product. This applicable variety substrates can be employed late-stage functionalization complex molecules.
Language: Английский
Citations
29
Chemical Science, Journal Year: 2024, Volume and Issue: 15(19), P. 7316 - 7323
Published: Jan. 1, 2024
A practical protocol for the stereoselective synthesis of unnatural α-amino acids is disclosed, using ubiquitous aliphatic alcohols as radical precursors to form acid backbone under redox-neutral photoredox-mediated conditions.
Language: Английский
Citations
6
ChemElectroChem, Journal Year: 2024, Volume and Issue: 11(13)
Published: May 2, 2024
Abstract Despite many recent efforts, the field of organic electrosyn‐thesis faces important challenges due to intricate nature heterogeneous redox processes, wide parameter space be explored and lack standardized methods. To overcome these limitations, we developed a cost‐effective high‐throughput electrochemical (HTE) reactor capable running 24 individually controlled parallel reactions. This system allows rapid testing parameters on given reaction, assessing not only yield but also reproducibility. Using hypervalent iodine‐mediated dearomatization phloretic acid as demonstration HTE capabilities, ran more than 200 electrosyntheses in different experimental conditions demonstrate effect such total charge transferred, current, electrode materials, electrolyte formulation concentration, mediator concentration technique oxidation. Notably, this report demonstrates that while catalytic amounts iodine can used successfully, reproducibility may affected, which calls for cautious approach when developing similar transformations. cyclic voltammetry, density functional theory, chronopotentiometry, Raman spectroscopy, shed light causes issue.
Language: Английский
Citations
6
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown
Published: Oct. 21, 2024
Abstract The catalytic deoxyamination of readily available 2‐arylethanols offers an appealing, simple, and straightforward means accessing β‐(hetero)arylethylamines biological interest. Yet, it currently represents a great challenge to synthetic chemistry. In most cases, the alcohol has be either pre‐activated in situ or converted into reactive carbonyl intermediate, limiting substrate scope for some methods. Examples direct dehydrative amination are thus still scarce. Here, we describe protocol based on synergy triflic acid hexafluoroisopropanol, which enables stereospecific broad array 2‐arylethanols, does not require any pre‐activation alcohol. This approach yields high value‐added products incorporating sulfonamide, amide, urea, aniline functionalities. addition, this was applied sulfidation 2‐arylethanols. Mechanistic experiments DFT computations indicate formation phenonium ions as key intermediates reaction.
Language: Английский
Citations
5
Synthesis, Journal Year: 2023, Volume and Issue: 55(18), P. 2993 - 2998
Published: Jan. 16, 2023
Abstract A direct electrochemical reductive approach for deoxygenation of alcohols has been developed in the presence substoichiometric amount AlCl3. The released Al ions from sacrificial anode could combine with chloride anion to regenerate Lewis acid.
Language: Английский
Citations
11