Electrochemical Late-Stage Functionalization

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

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Base‐Promoted Electrochemical Co^II‐catalyzed Enantioselective C−H Oxygenation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(21)

Published: March 20, 2023

Metalla-electrocatalyzed C-H oxygenation represents one of the most straightforward and sustainable approaches to access valuable oxygenated molecules. Despite significant advances, development enantioselective electrochemical reaction is very challenging remains elusive. Herein, we described first CoII -catalyzed alkoxylation. A broad range enantioenriched alkoxylated phosphinamides were obtained in good yields with excellent enantioselectivities (up 98 % yield >99 ee). An unusual cobalt(III) alcohol complex was prepared fully characterized, which proven be a key intermediate this alkoxylation reaction. Mechanistic studies revealed that oxidation CoIII CoIV facilitated by base whole process proceeded through cobalt(III/IV/II) catalytic cycle.

Language: Английский

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Electrochemical aromatic C–H hydroxylation in continuous flow

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: July 8, 2022

The direct hydroxylation of arene C-H bonds is a highly sought-after transformation but remains an unsolved challenge due to the difficulty in efficient and regioselective oxygenation high reactivity phenolic products leading overoxidation. Herein we report electrochemical arenes continuous flow for synthesis phenols. method characterized by broad scope (compatible with diverse electronic properties), mild conditions without any catalysts or chemical oxidants, excellent scalability as demonstrated production 1 mol (204 grams) one phenol products.

Language: Английский

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Direct C–H Hydroxylation of N-Heteroarenes and Benzenes via Base-Catalyzed Halogen Transfer

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9755 - 9767

Published: March 26, 2024

Hydroxylated (hetero)arenes are valued in many industries as both key constituents of end products and diversifiable synthetic building blocks. Accordingly, the development reactions that complement address limitations existing methods for introduction aromatic hydroxyl groups is an important goal. To this end, we apply base-catalyzed halogen transfer (X-transfer) to enable direct C–H hydroxylation mildly acidic N-heteroarenes benzenes. This protocol employs alkoxide base catalyze X-transfer from sacrificial 2-halothiophene oxidants aryl substrates, forming SNAr-active intermediates undergo nucleophilic hydroxylation. Key process use 2-phenylethanol inexpensive hydroxide surrogate that, after substitution rapid elimination, provides hydroxylated arene styrene byproduct. Use simple 2-halothiophenes allows 6-membered 1,3-azole derivatives, while a rationally designed 2-halobenzothiophene oxidant extends scope electron-deficient benzene substrates. Mechanistic studies indicate reversible, suggesting deprotonation, halogenation, steps operate synergy, manifesting unique selectivity trends not necessarily dependent on most position. The utility method further demonstrated through streamlined target molecule syntheses, examples regioselectivity contrast alternative methods, scalable recycling thiophene oxidants.

Language: Английский

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Electrolytic C–H Oxygenation via Oxidatively Induced Reductive Elimination in Rh Catalysis

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(11), P. 6590 - 6595

Published: May 20, 2021

Herein, we describe the development of a Rh-catalyzed C–H acyloxylation under mild electrolytic conditions. Anodic oxidation key rhodacyclic carboxylate intermediate was found to enable product-releasing C–O bond-forming reductive elimination process. An accumulation near electrode surface rationalized further induce desired bond formation, allowing an ambient catalytic oxygenation using stoichiometric amounts readily accessible carboxylic acid coupling partners.

Language: Английский

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Ruthenaelectro-catalyzed C–H acyloxylation for late-stage tyrosine and oligopeptide diversification

Chemical Science, Journal Year: 2022, Volume and Issue: 13(12), P. 3461 - 3467

Published: Jan. 1, 2022

Ruthenaelectro( ii / iv )-catalyzed intermolecular C–H acyloxylations of oligopeptides have been developed by the guidance key experimental, CV and computational insights.

Language: Английский

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Scalable selective electrochemical oxidation of sulfides to sulfoxides

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(12), P. 4772 - 4777

Published: Jan. 1, 2022

An electrochemical protocol for the selective oxidation of sulfides to sulfoxides has been developed in which NaCl plays a dual role: (1) as an electrolyte transformations and (2) redox mediator avoid sensitive functional groups.

Language: Английский

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Rhoda‐Electrocatalyzed Bimetallic C−H Oxygenation by Weak O‐Coordination

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(24), P. 13264 - 13270

Published: March 2, 2021

Rhodium-electrocatalyzed arene C-H oxygenation by weakly O-coordinating amides and ketones have been established bimetallic electrocatalysis. Likewise, diverse dihydrooxazinones were selectively accessed the judicious choice of current, enabling twofold functionalization. Detailed mechanistic studies experiment, mass spectroscopy cyclovoltammetric analysis provided support for an unprecedented electrooxidation-induced activation a rhodium catalysis manifold.

Language: Английский

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Dynamic weak coordination bonding of chlorocarbons enhances the catalytic performance of a metal–organic framework material

Journal of Materials Chemistry A, Journal Year: 2022, Volume and Issue: 10(44), P. 23499 - 23508

Published: Jan. 1, 2022

Solvents with weak coordination bonding ( e.g. , TCM and DCM) confined in the nanopores of a metal–organic framework undergo dynamic exchange stronger Lewis-basic solvents H 2 O), they lead to enhanced catalytic efficiency.

Language: Английский

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Al₂O₃‐coated BiVO₄ Photoanodes for Photoelectrocatalytic Regioselective C−H Activation of Aromatic Amines

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(52)

Published: Nov. 10, 2023

Photoelectrochemistry is becoming an innovative approach to organic synthesis. Generally, the current photoelectrocatalytic transformations suffer from limited reaction type, low conversion efficiency and poor stability. Herein, we develop efficient stable photoelectrode materials using metal oxide protective layer, with a focus on achieving regioselective activation of amine compounds. Notably, our photoelectrochemistry process implemented under mild conditions does not involve any directing groups, transition metals or oxidants. The results demonstrate that beyond photocatalysis electrocatalysis, photoelectrocatalysis exhibits high efficiency, remarkable repeatability good functional group tolerance, highlighting its great potential for applications.

Language: Английский

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