Tetravalent Spiroselenurane Catalysts: Intramolecular Se···N Chalcogen Bond-Driven Catalytic Disproportionation of H2O2 to H2O and O2 and Activation of I2 and NBS DOI
Monojit Batabyal, Aditya Upadhyay, Rahul Kadu

и другие.

Inorganic Chemistry, Год журнала: 2022, Номер 61(23), С. 8729 - 8745

Опубликована: Май 31, 2022

Chalcogen-bonding interactions have recently gained considerable attention in the field of synthetic chemistry, structure, and bonding. Here, three organo-spiroselenuranes, having a Se(IV) center with strong intramolecular Se···N chalcogen-bonded interaction, been isolated by oxidation respective bis(2-benzamide) selenides derived from an 8-aminoquinoline ligand. Further, synthesized spiroselenuranes, when assayed for their antioxidant activity, show disproportionation hydrogen peroxide into H2O O2 first-order kinetics respect to H2O2 first time any organoselenium molecules as monitored 1H NMR spectroscopy. Electron-donating 5-methylthio-benzamide ring-substituted spiroselenurane disproportionates at high rate 15.6 ± 0.4 × 103 μM min-1 constant 8.57 0.50 10-3 s-1, whereas 5-methoxy unsubstituted-benzamide spiroselenuranes catalyzed rates 7.9 0.3 2.9 constants 1.16 0.02 0.325 0.025 respectively. The evolved oxygen gas spiroselenurane-catalyzed disproportion has also confirmed chromatograph-thermal conductivity detector (GCTCD) portable digital polarographic dissolved probe. Additionally, exhibit thiol peroxidase activities reduction benzenethiol co-reductant UV-visible Next, bonded explored catalysts iodolactonization bromination arenes. activated I2 toward alkenoic acids under base-free conditions. Similarly, efficient chemo- regioselective monobromination various arenes NBS achieved. Mechanistic insight reactions 77Se NMR, mass spectrometry, spectroscopy, single-crystal X-ray theoretical (DFT, NBO, AIM) studies. It seems that highly electrophilic nature selenium is attributed presence interaction vacant coordination site crucial activation H2O2, I2, NBS. reaction tetravalent would lead octahedral-Se(VI) intermediate, which reduced back due thermodynamic instability its highest state N-donor atom.

Язык: Английский

Main Group Redox Catalysis of Organopnictogens: Vertical Periodic Trends and Emerging Opportunities in Group 15 DOI
Jeffrey M. Lipshultz, Gen Li, Alexander T. Radosevich

и другие.

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(4), С. 1699 - 1721

Опубликована: Янв. 19, 2021

A growing number of organopnictogen redox catalytic methods have emerged-especially within the past 10 years-that leverage plentiful reversible two-electron chemistry Group 15. The goal this Perspective is to provide readers context understand dramatic developments in catalysis over decade with an eye toward future development. An exposition fundamental differences atomic structure and bonding pnictogens, thus molecular electronic compounds, presented establish backdrop against which reactivity-and ultimately catalysis-is framed. deep appreciation these underlying periodic principles informs understanding differing modes evokes key challenges field moving forward. We close by addressing forward-looking directions likely animate area years come. What new manifolds can be developed through creative catalyst reaction design that take advantage intrinsic reactivity pnictogens drive discoveries catalysis?

Язык: Английский

Процитировано

216
Recent progress in selenium-catalyzed organic reactions DOI
Li‐Xiong Shao, Yiming Li, Jian‐Mei Lu

и другие.

Organic Chemistry Frontiers, Год журнала: 2019, Номер 6(16), С. 2999 - 3041

Опубликована: Янв. 1, 2019

Selenium-based catalysts, including organo- and inorganoselenium ones, in organic synthesis the recent decade are reviewed.

Язык: Английский

Процитировано

189
Electrifying green synthesis: recent advances in electrochemical annulation reactions DOI Creative Commons
Guilherme M. Martins, Geórgia C. Zimmer, Samuel R. Mendes

и другие.

Green Chemistry, Год журнала: 2020, Номер 22(15), С. 4849 - 4870

Опубликована: Янв. 1, 2020

Herein, electrochemical annulations involving mediators and mediator-free conditions have been discussed. Also, the use of sacrificial electrodes has explored.

Язык: Английский

Процитировано

112
Radical selenation of C(sp3)–H bonds to asymmetric selenides and mechanistic study DOI
Xin Wang,

Jia Lei,

Sa Guo

и другие.

Chemical Communications, Год журнала: 2022, Номер 58(10), С. 1526 - 1529

Опубликована: Янв. 1, 2022

Selenides are important structural motifs with a broad range of biological activities and versatile transformational abilities. In this study, novel mild method was developed for the facile synthesis asymmetric selenides under metal-free conditions. The key features reaction include good functional-group tolerance, use readily available reagents cheap, low-toxicity solvent, amenability to gram-scale synthesis. results preliminary radical-trapping experiments kinetic isotope effect study support radical process.

Язык: Английский

Процитировано

39
Electrophilic Selenium-Catalyzed Desymmetrizing Cyclization to Access P-Stereogenic Heterocycles DOI

Zhichao Qi,

Yuke Li, Juan Wang

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(20), С. 13301 - 13309

Опубликована: Окт. 2, 2023

The construction of phosphorus stereocenters under metal-free conditions remains a formidable challenge. Herein, we report mechanistically distinct chiral electrophilic selenium catalysis-enabled desymmetrizing cyclization to access valuable phosphorus-stereogenic heterocycles with high efficiency. This ambient temperature method affords broad range compounds that bear phenolic hydroxyl group as useful synthetic handle and, thus, enriches the toolbox for rapid generation molecular complexity. control experiments and DFT calculations indicate dual-hydrogen-bonding bridge formed between substrate TfO– anion plays crucial role in determining enantioselectivity transformation.

Язык: Английский

Процитировано

28
Electrochemical Regioselective C(sp2)–H Selenylation and Sulfenylation of Substituted 2-Amino-1,4-naphthoquinones DOI
Pintu Karmakar, Indrajit Karmakar, D. R. PAL

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(2), С. 1049 - 1060

Опубликована: Янв. 4, 2023

A straightforward and efficient electrochemical method for regioselective C(sp2)-H selenylation sulfenylation of substituted 2-amino-1,4-naphthoquinones has been unearthed. This oxidative cross-coupling reaction avoids using transition metal catalysts, oxidants, high temperatures. The other notable advantages this protocol are the tolerance diverse functional groups, mild conditions at ambient temperature, energy efficiency, good to excellent yields, short times (in minutes), gram-scale applicability, eco-friendliness.

Язык: Английский

Процитировано

22
Asymmetric Synthesis with Organoselenium Compounds – The Past Twelve Years DOI Creative Commons

Jessica T. Stadel,

Thomas G. Back

Chemistry - A European Journal, Год журнала: 2024, Номер 30(21)

Опубликована: Янв. 11, 2024

Abstract The discovery and synthetic applications of novel organoselenium compounds their reactions proceeded rapidly during the past fifty years such processes are now carried out routinely in many laboratories. At same time, growing demand for new enantioselective provided challenges. convergence selenium chemistry asymmetric synthesis led to key developments 1970s, although majority early work was based on stoichiometric processes. More recently, greater emphasis has been placed greener catalytic variations, along with a deeper understanding mechanisms. present review covers literature this field from 2010 2023 encompasses mediated by chiral selenium‐based reagents, auxiliaries, especially, catalysts. Protocols achiral conjunction other species catalysts, as well that controlled substrates, also included.

Язык: Английский

Процитировано

10
Visible-Light-Driven Synergistic Se/Fe Catalysis for the Synthesis of 2-Aminoquinoline Derivatives DOI

Yan‐Ling Ji,

Hong Wang,

Xiang‐Hong He

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 3, 2025

A visible-light-driven Se/Fe synergistic catalytic reaction between isocyanides and amines has been developed, employing air as the terminal oxidant. This efficient strategy offers facile access to 2-aminoquinoline scaffolds. The use of cost-effective readily available Fe(OTf)3 modulates selenium catalyst's oxidation state, enhancing method's environmental friendliness practicality. protocol is further distinguished by its good yields, broad substrate scope, mild conditions.

Язык: Английский

Процитировано

1
Organoselenium-Catalyzed Oxidative Allylic Fluorination with Electrophilic N–F Reagent DOI

Ruizhi Guo,

Jiachen Huang, Xiaodan Zhao

и другие.

ACS Catalysis, Год журнала: 2017, Номер 8(2), С. 926 - 930

Опубликована: Дек. 29, 2017

An efficient route of organoselenium-catalyzed oxidative allylic fluorination has been developed. In this transformation, bulky electrophilic fluorinating reagent N-fluoro-2,4,6-trimethylpyridinium triflate (TMFP-OTf) was employed as the oxidant and fluorine source. Notably, TEMPO an additive affects leads to better substrate scope excellent functional group tolerance. By protocol, a variety fluorides were synthesized in good yields. The obtained could be converted into vinyl efficiently presence appropriate base.

Язык: Английский

Процитировано

75
Ruthenium(II)‐Catalyzed C−H Chalcogenation of Anilides DOI
Wenbo Ma,

Zhengyun Weng,

Torben Rogge

и другие.

Advanced Synthesis & Catalysis, Год журнала: 2017, Номер 360(4), С. 704 - 710

Опубликована: Ноя. 27, 2017

Abstract Ruthenium‐catalyzed C−H chalcogenations of anilides with readily available diselenides and disulfides have been achieved. Our strategy features ample substrate scope, affording the mono‐ ortho selenylated thiolated complete site selectivity control high catalytic efficacy. Detailed mechanistic studies provide strong support for a facile base‐assisted internal electrophilic substitution (BIES) metalation event. magnified image

Язык: Английский

Процитировано

71