Flexible Coordination of SacNac Ligands in Iridium Complexes and their Application to Catalytic Hydroboration

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 27(30)

Published: Aug. 28, 2024

Abstract Herein, we report the synthesis and characterization of a small family Ir(I) Ir(III) complexes supported by β‐thioketoiminates ( SacNac ) ligands. All were fully characterized IR, 1D 2D NMR, Elemental Analysis (e.a.) experiments. X‐ray diffraction studies carried out to corroborate structure compounds [Ir(cod)( )] 1 (cod=1,5‐cyclooctadiene), [Ir(dmb)( 2 (dmb=2,3‐dimethyl‐1,3‐butadiene) [IrCp*( ‐H)(Cl) ] 8 (Cp*=pentamethyl‐cyclopentadienyl). Complexes are species have square‐planar geometry in solid state, with bond angles distances that suggest semi‐aromaticity six‐membered ring. To best our knowledge, first mono‐coordination mode ligand via sulfur atom complex . Also, application iridium‐ as catalytic precursors hydroboration reactions, where give results.

Language: Английский

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Catalytic hydroboration of aldehydes and ketones with an electron-rich acyclic metallasilylene

Chemical Science, Journal Year: 2024, Volume and Issue: 15(11), P. 4161 - 4170

Published: Jan. 1, 2024

Catalytic hydroboration of aldehydes and ketones is achieved with alkoxysilylene 2. Quantum chemical calculations gave insights into the energetics its formation provide possible catalytic reaction mechanism.

Language: Английский

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Markovnikov Selective Hydroboration of Aryl Alkenes Catalyzed by Quaternary Ammonium Salts

Published: March 27, 2024

Despite recent advancements in the development of catalytic Markovnikov-selective hydroboration alkenes, metal-free procedure has long remained an unsolved challenge. Here, we report organocatalytic hy-droboration aryl alkenes using a commercially available quaternary ammonium catalyst. The method is operationally simple, scalable, and compatible with wide variety substrates it can be successfully applied synthesis active pharmaceutical ingredients (API) such as Chlorphenoxamine. Through in-depth experimental DFT studies, elucidate nuanced understanding mechanism regioselectivity this reaction.

Language: Английский

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Metal‐Free Ammonia Borane‐Catalyzed Hydroboration of Lactones and Esters to Alcohols

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(20)

Published: June 17, 2024

Abstract Herein we describe an efficient methodology for metal‐free hydroborative cleavage of lactones and esters with HBPin (Pin=pinacol) to the corresponding alcohol derivatives using ammonia borane as a pre‐catalyst. The reactions proceed under mild conditions, can be performed in solvent‐free manner, do not require inert atmosphere. Combined experimental computational mechanistic studies suggest novel mechanism that involves μ‐aminodiboranes catalytically active species.

Language: Английский

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Saturated (C(sp3) B) Boronic Acid Derivatives

Elsevier eBooks, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Language: Английский

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Cobalt-Catalyzed Borylative Reduction of Azobenzenes to Hydrazobenzenes via a Diborylated-Hydrazine Intermediate

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(13), P. 9265 - 9274

Published: June 20, 2024

Cobalt-catalyzed borylative reduction of azobenzenes using pinacolborane is developed. The simple cobalt chloride catalyst and reaction conditions make this protocol attractive for hydrazobenzene synthesis. This shows good functional group compatibility can be readily scaled up to the gram scale. Preliminary mechanistic studies clarified proton source hydrazine products. cobalt-catalyzed azobenzene provides a practical prepare synthetically useful diborylated hydrazines.

Language: Английский

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2-Anilidomethylpyridine-Derived Three-Coordinate Zinc Hydride: The Journey Unveils Anilide Backbone’s Reactive Nature

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 63(1), P. 739 - 751

Published: Dec. 21, 2023

Low-coordinate heteroleptic zinc hydrides are catalytically important but rare and synthetically challenging. We herein report three-coordinate monomeric hydride on a 2-anilidomethylpyridine framework (NNL). The synthetic success comes through systematically screening few different routes from precursors. During the process, ligand's anilide backbone interestingly appears to be more reactive than Zn's terminal site electrophilic Lewis Brønsted acids. proligand NNLH reacts with [Zn{N(SiMe3)2}2] ZnEt2 give [(NNL)ZnA] (A = N(SiMe3)2 (1), Et(2)). Both inert PhSiH3 H2 react HBpin only internal Zn–Nanilide bond borylated ligand NNLBpin (3). reactions of 1 2 Ph3EOH (E C, Si) afford series divergent compounds like [(NNLH)Zn(OSiPh3)2] (4), [Zn3(OSiPh3)4Et2] (5), [EtZn(OCPh3)] (6). But in all cases, it is invariably protonated by –OH equal or higher preference Zn–N Zn–C bonds. A DFT analysis rationalizes origin such reactivity pattern. Realizing that an acid-free route might key, reacting [(NNL)Li] ZnBr2 gives [(NNL)Zn(μ-Br)]2 (7), which successively treating KOSiPh3 desired [(NNL)ZnH] (8) as monomer Zn–H bond. Estimating steric 8 shows openness coordination sphere, criterion for efficient catalysis. This positive influence pyridyl sidearm reflected 8's superior activity hydroborating PhC(O)Me comparison Jones' two-coordinate anilido hydride.

Language: Английский

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Regioselective Rhodium‐Catalyzed 1,2‐Hydroboration of Pyridines and Quinolines Enabled by the Tris(8‐quinolinyl)phosphite Ligand**

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(29)

Published: Aug. 7, 2023

Abstract A Rh(I) complex [κ 2 ( P,N )‐{P(Oquin) 3 }RhCl(PPh )] 1 ) bearing the ligand tris(8‐quinolinyl)phosphite, P(Oquin) , has been synthesized and structurally characterized. The molecular structure of shows that acts as a bidentate chelate ligand. Reactivity studies reveal triphenylphosphine can be replaced by Pcy or removed upon oxidation with concomitant coordination second 8‐quinolyl unit . In addition, Rh(III) [RhCl {OP(Oquin) }] ), resulting from treating either wet CDCl or, sequentially, HCl water, was identified X‐ray diffraction analysis. Complex catalyzes 1,2‐regioselective hydroboration pyridines quinolines, affording N ‐boryl‐1,2‐dihydropyridines (1,2‐BDHP) ‐boryl‐1,2‐hydroquinolines (1,2‐BDHQ) in high yield (up to >95 %) turnover numbers (TONs) up 130. system tolerates variety substrates different electronic steric nature. comparison other transition‐metal‐based catalysts, this is efficient at low catalyst loading without requirement base additives.

Language: Английский

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Synthesis and Structural Characterization of 2,2’-Bipyridine Zinc Formate: Analysis of Formate Bonding and Hydrosilylation of CO2 and Carbonyl Compounds

Journal of Organometallic Chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 123471 - 123471

Published: Dec. 1, 2024

Language: Английский

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Gold(I)-catalyzed intramolecular C(sp3)—H bond functionalization

Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 16, 2024

Abstract The merger of two the most rapidly growing fields in catalysis, namely gold-catalysis and C–H activation/functionalization has resulted major breakthroughs, affording unprecedented transformations. This review covers relevant contributions this field during last 10 years, restricted to intramolecular functionalization C(sp3)–H bonds. 1 Introduction 2 Carbene/Vinylidene Insertion 3 [1,5]-H Shift 4 Gold-Stabilized Vinyl Cation Mediated 5 Summary Outlook

Language: Английский

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