Highly efficient one-pot multi-directional selective hydrogenation and N-alkylation catalyzed by Ru/LDH under mild conditions

Applied Catalysis A General, Год журнала: 2020, Номер 596, С. 117536 - 117536

Опубликована: Март 19, 2020

Язык: Английский

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Iron-Catalyzed sp³ C–H Alkylation of Fluorene with Primary and Secondary Alcohols: A Borrowing Hydrogen Approach

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(22), С. 16223 - 16241

Опубликована: Авг. 23, 2024

The utilization of earth-abundant, cheap, and nontoxic transition metals in important catalytic transformations is essential for sustainable development, iron has gained significant attention as the most abundant metal. A mixture FeCl2 (3 mol %), phenanthroline (6 KOtBu (0.4 eqivalent) was used an effective catalyst sp3 C–H alkylation fluorene using alcohol a nonhazardous alkylating partner, eco-friendly water formed only byproduct. substrate scope includes wide range substituted fluorenes benzyl alcohols. reaction equally with challenging secondary alcohols unactivated aliphatic Selective mono-C9-alkylation yielded corresponding products good isolated yields. Various postfunctionalizations C-9 alkylated were performed to establish practical utility this alkylation. Control experiments suggested homogeneous path involving borrowing hydrogen mechanism formation subsequent reduction 9-alkylidene intermediate.

Язык: Английский

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Bulky Diphosphine Acetate Ruthenium Complexes: Synthesis and Catalytic Activity in Ketone Transfer Hydrogenation and Alkyne Dimerization

Organometallics, Год журнала: 2020, Номер 39(17), С. 3180 - 3193

Опубликована: Авг. 18, 2020

Several mononuclear ruthenium complexes containing bulky diphosphines have been easily prepared from acetate precursors. The cyclohexyl complex [Ru(η2-OAc)2(DCyPF)] (1-cy; DCyPF = 1,1′-bis(dicyclohexylphosphino)ferrocene) is synthesized [Ru(η2-OAc)2(PPh3)2] and in toluene at reflux, whereas the ethylenediamine (en) derivatives trans-[Ru(η1-OAc)2(PP)(en)] (PP 1,1′-bis(diisopropylphosphino)ferrocene (DiPPF) (2), (3)) obtained a one-pot reaction [Ru(η2-OAc)2(PPh3)2], PP, en n-heptane. Treatment of isopropylphosphine [Ru(η2-OAc)2(DiPPF)] (1-ip) with 2-(aminomethyl)pyridine (ampy) methanol affords isolation mixture cationic [Ru(η2-OAc)(DiPPF)(ampy)]OAc (5a) cis-[Ru(η1-OAc)2(DiPPF)(ampy)] (5b) (4/1 molar ratio), via trans-[Ru(η1-OAc)2(DiPPF)(ampy)] (4) characterized low temperature. analogous compound trans-[Ru(η1-OAc)2(DCyPF)(ampy)] (6), ampy heptane, slowly converts into [Ru(η2-OAc)(DCyPF)(ampy)]OAc (7) RT. monocarbonyl [Ru(η1-OAc)(η2-OAc)(PP)(CO)] 1,3-bis(cyclohexylphosphino)propane (DCyPP) (8), (R)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyldicyclohexylphosphine (Josiphoscy) (9)) are [Ru(η1-OAc)(η2-OAc)(PPh3)2(CO)] suitable diphosphine. [Ru(η1-OAc)(η2-OAc)(DiPPF)(CO)] (10) phenylacetylene presence pyridine leads to alkynyl [Ru(η2-OAc)(C≡CPh)(DiPPF)(CO)] (11), by X-ray diffraction analysis. Protonation 10 2 equiv TFA RT gives [Ru(η1-OCOCF3)(η2-OCOCF3)(DiPPF)(CO)] (12). dicarbonyl trans,cis-[Ru(η1-OAc)2(DiPPF)(CO)2] (13) 1-ip CO (1 atm) CH2Cl2, isomer cis,cis-[Ru(η1-OAc)2(DiPPF)(CO)2] (14) can be carbonylation 10. When 13 heated solid state, formed decarbonylation. These promote transfer hydrogenation acetophenone 2-propanol (S/C 1000–2000) NaOiPr (2 mol %), affording TOF value up 81000 h–1 for 9 30 °C. Complex catalyzes head-to-head dimerization terminal alkynes 1,4-enynes reflux high stereoselectivity kinetic Z isomer.

Язык: Английский

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Half-sandwich ruthenium-carbene catalysts: Synthesis, characterization, and catalytic application in the N-alkylation of amines with alcohols

Inorganica Chimica Acta, Год журнала: 2019, Номер 498, С. 119163 - 119163

Опубликована: Сен. 20, 2019

Язык: Английский

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Ruthenium Catalyzed N‐Alkylation of Cyclic Amines with Primary Alcohols

European Journal of Organic Chemistry, Год журнала: 2020, Номер 2020(20), С. 3030 - 3040

Опубликована: Апрель 16, 2020

A robust alcohol amination protocol using common saturated amines and primary alcohols as starting materials is described. The reactions are catalyzed by combination of dichloro( p ‐cymene)ruthenium(II) dimer precatalyst with triphenylphosphine ligand, the excess substrate or toluene functioning solvent. catalyst ligand residues can be precipitated from reaction media addition hexane cold diethyl ether, followed precipitation isolation product a hydrochloride salt.

Язык: Английский

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N-Alkylation of aromatic amines with alcohols by using a commercially available Ru complex under mild conditions

RSC Advances, Год журнала: 2023, Номер 13(49), С. 34847 - 34851

Опубликована: Янв. 1, 2023

An N -alkylation procedure has been developed under very mild conditions using a known commercially available Ru-based catalyst.

Язык: Английский

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