Photocatalytic decarboxylation of free carboxylic acids and their functionalization

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(72), P. 9645 - 9658

Published: Jan. 1, 2024

This highlight article summarizes the complete development of photodecarboxylative functionalization free carboxylic acids via a concerted single electron transfer (SET) or energy (ET) pathways.

Language: Английский

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Iron-catalyzed decarboxylative radical addition to chiral azomethine imines upon visible light

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(49), P. 6316 - 6319

Published: Jan. 1, 2024

Eco-efficient LMCT based redox-neutral iron-catalyzed decarboxylative radical addition to chiral azomethine imines upon visible light.

Language: Английский

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Graphitic Carbon Nitride as a Photocatalyst for Decarboxylative C(sp2)–C(sp3) Couplings via Nickel Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: May 29, 2024

The development of robust and reliable methods for the construction C(sp

Language: Английский

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Transformative ligand effects in Fe-photocatalyzed Giese-type additions

Chem Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 101131 - 101131

Published: Oct. 1, 2024

Language: Английский

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C(sp³)–H Carboxylation via Carbene/Photoredox Cooperative Catalysis

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(2), P. 1287 - 1293

Published: Jan. 7, 2025

C(sp3)–H bond functionalization is a powerful strategy for the synthesis of organic compounds due their abundance in simple starting materials. Photoredox catalysis has led to diverse array enabling activation strategies; however, general platform direct carboxylic acid derivatives remains elusive. Disclosed herein development cooperative NHC/photoredox-catalyzed esterification transformation. This method enables access benzylic, α-heteroatom, and formal β-esterification products moderate high yields under mild reaction conditions.

Language: Английский

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Direct C1 Homologation of Carboxylic Acids: Free Radical Approach Enabled by Acridine Catalysis

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Homologation of carboxylic acids with a tosylhydrazone reagent is described. The reaction performed using dual acridine/decatungstate photocatalytic system.

Language: Английский

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Activation of Molecular Oxygen and Selective Oxidation with Metal Complexes

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 21, 2025

ConspectusSelective oxidation with molecular oxygen is one of the most appealing approaches to functionalization organic molecules and, yet at same time, challenging reactions facing synthesis due poor selectivity control. Molecular a green and inexpensive oxidant, producing water as only byproduct in oxidation. Not surprisingly, it has been used manufacturing many commodity chemicals industry. It also nature's choice oxidant drives variety critical life various other biologic processes. While past decades have witnessed great progress understanding, both structurally mechanistically, how nature exploits metalloenzymes, i.e., monooxygenases dioxygenases, tackle some reactions, e.g., methane methanol, there are small number well-defined, man-made metal complexes that reported enable selective compounds more relevant fine chemical pharmaceutical synthesis.In 10 years or so, our laboratories developed several transition shown they capable catalyzing under 1 atm O2. Thus, we an Fe(II)-bisimidazolidinyl-pyridine complex catalyzes oxygenation C–H bonds ethers concomitant release hydrogen gas instead water, when iron center replaced Fe(III), oxidative cleavage C═C olefins becomes feasible. To address low activity oxidizing less active olefins, Mn(II)-bipyridine complex, which aliphatic C–C diols, carboxyl units carboxylic acids visible light irradiation. Light necessary cleave off-cycle, inactive manganese dimer into catalytically Mn═O oxo species. Furthermore, found binuclear salicylate-bridged Cu(II) enables tetrahydroisoquinolines well bond cleavage, catalytic vitamin B1 analogue brought in, lactams takes place via carbene catalysis. Still further, readily accessible Rh(II)-terpyridine alcohols, being water-soluble, catalyst can be easily separated reused multiple times. In addition, recently unearthed simple protocol allows waste polystyrene depolymerized isolable, valuable chemicals. A cheap Brønsted acid acts catalyst, activating singlet state through complexation polymer irradiation, thereby depolymerizing polymer.

Language: Английский

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Electrochemical Conversion of Carboxylic Acids to Terminal Alkenes Enabled by Dialkyl Phosphate Electrolyte

Tetrahedron, Journal Year: 2025, Volume and Issue: 176, P. 134560 - 134560

Published: Feb. 24, 2025

Language: Английский

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Spectroscopic and Nonlinear Optical Insights of Picolinaldehyde‐Based Materials: Experimental and DFT Approach

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(12)

Published: March 1, 2025

Abstract Herein, a series of picolinaldehyde‐based materials ( DMeP‐TFMP ) were synthesized, via the decarboxylative Suzuki coupling reaction using readily accessible 2‐formyl‐6‐pyridinoic acid, to investigate their nonlinear optical (NLO) properties. Various spectroscopic techniques like UV–vis, FT‐IR, ¹H‐NMR, and ¹ 3 C‐NMR employed elucidate molecular structures synthesized chromophores. Further, density functional theory (DFT) time dependent (TD‐DFT) calculations at M06/6‐311G (d,p) level conducted assess frontier orbitals (FMOs), absorption properties, insights. The DMeP displayed minimal band gap (4.390 eV among studied compounds with highest bathochromic shift (340.476 nm). states (DOS) transition matrix (TDM) analyses validated charge transitions from valance conduction band. All exhibited enhanced exciton dissociation rates because low binding energy values E b = 0.525 0.572 ). Furthermore, electron‐hole analysis revealed distribution electron hole densities across different atoms in compounds, indicating significant creation specific atomic sites. notable linear polarizability that is, (⟨α⟩ 2.59 × 10⁻ 2 ‐3.62 esu ), first hyperpolarizability β tot 2.87 ⁰−16.4 ⁰ second γ 1.93 ⁵‐8.44 ⁵ highlighting potential as efficient for advanced NLO applications.

Language: Английский

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Configuration Retention in P-Trifluoromethyl Phosphine Enabled Rh(I)-Catalyzed Decarbonylative Coupling of Carboxylates and Boroxines

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

As compared with asymmetric catalysis, the memory of chirality provides another promising strategy to introduce chiral centers in light numerous starting materials that can be accessed. Decarboxylative coupling has become an important for C-C or C-X bond formation over decades development its versatility and low cost structural diversity carboxylic acids. However, more general configuration retention this transformation seldom been studied. Here, we report a novel π acceptor-type ligand P-trifluoromethyl phosphine enabled Rh(I)-catalyzed decarbonylative carboxylates boroxines. The α-carbon fully retained chiral, cis-, trans-substrates. Several phosphine-Rh(I) carbonyl complexes were prepared their v(CO) values known complexes, which indicated π-accepting property is reaction.

Language: Английский

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