Thiocarboxylate and Acid Chloride Mediated Generation of Nitric Oxide from a Dinickel(II)-Bis(ONO) Complex Involving the Formation of Perthionitrite and O-Nitrosyl Carboxylate DOI
Md. Kamal Hossain, Arindam Basak, Amit Majumdar

et al.

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

Published: April 22, 2025

A detailed study for the generation of nitric oxide (NO) upon reaction a binuclear Ni(II)-bis(ONO) complex with carboxylic acids (RCOOH, R = Me, Ph), thiols (RSH, Ph, p-F-C6H4), benzeneselenol (PhSeH), thiocarboxylates (RC(O)S-, thiocarboxylic (RC(O)SH, and acid chlorides (RC(O)Cl, Ph) has been presented. The reactions thiols/selenols give access to unusual dinickel(II)-nitrito-thiolato/selenolato complexes, while RC(O)S-, RC(O)SH, RC(O)Cl offer new mechanistic insights into perthionitrite (SSNO-) O-nitrosyl carboxylates (RC(O)ONO), well-known NO-carrying species in biology. Interestingly, RC(O)S- involved nucleophilic attack latter coordinated NO2- generate SSNO-, proceeds via hitherto unknown carbonyl carbon RC(O)ONO, which, turn, produces NO. present comparative thus demonstrates metal-coordinated investigations supported by molecular structure determinations spectroscopic studies establishes nitrite be highly efficient method NO excellent yield.

Language: Английский

Copper-Catalyzed Enantioselective [4π + 2σ] Cycloaddition of Bicyclobutanes with Nitrones DOI

Xuan-Ge Zhang,

Zi-Yang Zhou,

Jiaxin Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 25, 2024

The selective construction of bridged bicyclic scaffolds has garnered increasing attention because their extensive use as saturated bioisosteres arene in pharmaceutical industry. However, sharp contrast to racemic counterparts, assembling chiral structures an enantioselective and regioselective manner remains challenging. Herein, we describe our protocol for constructing 2-oxa-3-azabicyclo[3.1.1]heptanes (BCHeps) by [4π + 2σ] cycloadditions bicyclo[1.1.0]butanes (BCBs) nitrones taking advantage a copper(II) complex Lewis acid catalyst. This method features mild conditions, good functional group tolerance, high yield (up 99%), excellent enantioselectivity 99% ee). Density theory (DFT) calculation elucidates the origin reaction's mechanism BCB activation Cu(II) complex.

Language: Английский

Citations

20
Dual Transition Metal Electrocatalysis: Direct Decarboxylative Alkenylation of Aliphatic Carboxylic Acids DOI
Jiaqing Lu, Yan Yao, Liubo Li

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(49), P. 26774 - 26782

Published: Nov. 29, 2023

Direct decarboxylative alkenylation of widely available aliphatic carboxylic acids with vinyl halides for the synthesis alkenes all substitution patterns has been accomplished by means Ce/Ni dual transition metal electrocatalysis. The reactions employ alkyl as limiting reagents and exhibit a broad scope respect to both coupling partners. Notably, simple primary could be readily engaged carbon-centered radical precursors in reaction. This new protocol successfully demonstrated direct modification naturally occurring complex is amenable enantioselective arylacetic acid. Mechanistic studies, including series controlled experiments cyclic voltammetry data, allow us probe key intermediates pathway

Language: Английский

Citations

31
A decarbonylative approach to alkylnickel intermediates and C(sp 3 )-C(sp 3 ) bond formation DOI
Zhidao Huang, Michelle E. Akana, Kyana M. Sanders

et al.

Science, Journal Year: 2024, Volume and Issue: 385(6715), P. 1331 - 1337

Published: Sept. 19, 2024

The myriad nickel-catalyzed cross-coupling reactions rely on the formation of an organonickel intermediate, but limitations in forming monoalkylnickel species have limited options for C(sp 3 ) cross-coupling. monoalkylnickel(II) from abundant carboxylic acid esters would be valuable, derivatives are primarily decarboxylated to form alkyl radicals that lack correct reactivity. In this work, we disclose a facile oxidative addition and decarbonylation sequence forms intermediates through nonradical process. key ligand, bis(4-methylpyrazole)pyridine, accelerates decarbonylation, stabilizes alkylnickel(II) destabilizes off-cycle nickel(0) carbonyl species. utility new reactivity )-C(sp bond is demonstrated reaction challenging by purely radical methods—the selective primary with iodides.

Language: Английский

Citations

12
Synthesis and Suzuki–Miyaura Cross-Coupling of Alkyl Amine-Boranes. A Boryl Radical-Enabled Strategy DOI Creative Commons
Cornelia S. Buettner,

Chiara Stavagna,

Michael J. Tilby

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(34), P. 24042 - 24052

Published: Aug. 13, 2024

Alkyl organoborons are powerful materials for the construction of C(

Language: Английский

Citations

9
Dual Acridine/Decatungstate Photocatalysis for the Decarboxylative Radical Addition of Carboxylic Acids to Azomethines DOI

Zakhar M. Rubanov,

Vitalij V. Levin, Alexander D. Dilman

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3174 - 3178

Published: April 8, 2024

A concept for the dual use of acridine and tetrabutylammonium decatungstate photocatalysts in reactions carboxylic acids is proposed. Imines generated situ from aldehydes p-methoxyaniline, as well other azomethines, were used radical acceptors. The role believed to facilitate turnover photocatalyst by means hydrogen atom transfer.

Language: Английский

Citations

8
Green Metrics and Sustainability in Photocatalysis DOI Creative Commons
Arianna Quintavalla, Davide Carboni, Marco Lombardo

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(14)

Published: Jan. 5, 2024

Abstract In the past century, significant advancements in synthetic chemistry undeniably contributed to wellness of mankind, from development new drugs design materials for energy production and storage. However, this technological progress has also brought forth challenges, emphasizing urgent need rethink more environmentally friendly approaches. Review a critical comprehensive analysis sustainability preparation commonly used photocatalysts is performed, by employing mass‐based metrics. Additionally, comparative evaluation made between some selected photocatalytic protocols traditional reactions not relying on light. The objective quantitatively evaluate claims greenness associated with photocatalysis, exploring real impact procedures waste generation. This quantitative approach provides insights into broader concept sustainable processes, challenging assumptions encouraging rigorous green catalysis. Furthermore, toxicity involved species availability required chemical elements commented provide global perspective analyzed transformations. results shed light true environmental footprint photocatalysis reveal that notion can sometimes be overstated.

Language: Английский

Citations

7
A General Iron‐Catalyzed Decarboxylative Oxygenation of Aliphatic Carboxylic Acids DOI Creative Commons
Luca Mareen Denkler,

Meghana Aladahalli Shekar,

Tak Shing Jason Ngan

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 13, 2024

Abstract We report an iron‐catalyzed decarboxylative C(sp 3 )−O bond‐forming reaction under mild, base‐free conditions with visible light irradiation. The transformation uses readily available and structurally diverse carboxylic acids, iron photocatalyst, 2,2,6,6‐tetramethylpiperidine 1‐oxyl (TEMPO) derivatives as oxygenation reagents. process exhibits a broad scope in acids possessing wide range of stereoelectronic properties functional groups. developed was applied to late‐stage series bio‐active molecules. leverages the ability complexes generate carbon‐centered radicals directly from by photoinduced carboxylate‐to‐iron charge transfer. Kinetic, electrochemical, EPR, UV/Vis, HRMS, DFT studies revealed that TEMPO has triple role reaction: reagent, oxidant turn over Fe‐catalyst, internal base for acid deprotonation. obtained adducts represent versatile synthetic intermediates were further engaged C−C C‐heteroatom reactions using commercial organo‐photocatalysts nucleophilic

Language: Английский

Citations

7
Nickel‐Catalyzed Highly Selective Radical C−C Coupling from Carboxylic Acids with Photoredox Catalysis DOI
Bo Ling,

Shunruo Yao,

Shengmao Ouyang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 24, 2024

Controlling the cross-coupling reaction between two different radicals is a long-standing challenge due to process occurring statistically, which would lead three products, including homocoupling products and one product. Generally, selectivity achieved by persistent radical effect (PRE) that requires presence of transient radical, thus resulting in limited precursors. In this paper, highly selective alkyl with acyl construct C(sp

Language: Английский

Citations

7
Direct decarboxylative Giese amidations: photocatalytic vs. metal- and light-free DOI Creative Commons

David M. Kitcatt,

Katie A. Scott,

Elena Rongione

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(36), P. 9806 - 9813

Published: Jan. 1, 2023

A direct intermolecular decarboxylative Giese amidation reaction from bench stable, non-toxic and environmentally benign oxamic acids has been developed, which allows for easy access to 1,4-difunctionalised compounds are not otherwise readily accessible. Crucially, a more general acceptor substrate scope is now possible, renders the applicable complex substrates such as natural products chiral building blocks. Two different photocatalytic methods (one via oxidative other reductive quenching cycles) one metal- light-free method were developed flexibility provided by conditions proved be crucial enabling scope.

Language: Английский

Citations

15
Titanium in photocatalytic organic transformations: current applications and future developments DOI
Jia‐Lin Tu, Binbin Huang

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(33), P. 6650 - 6664

Published: Jan. 1, 2024

Titanium, as an important transition metal, has garnered extensive attention in both industry and academia due to its excellent mechanical properties, corrosion resistance, unique reactivity organic synthesis. In the field of photocatalysis, titanium-based compounds such titanium dioxide (TiO

Language: Английский

Citations

6