Bidentate Ru(<scp>ii</scp>)-NC complexes as catalysts for the dehydrogenative reaction from primary alcohols to carboxylic acids

Gong, Dawei; Hu, Bowen; Chen, Dafa

doi:10.1039/c9dt01414d

Cited by 29 publications

(17 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…(1) [15] Together with the experimental results and the related literatures, [8][9][10][11][12][13]17] a possible mechanism is proposed in Scheme 4. Excess of Hg (Hg : Ru = 400 : 1) did not influence the conversion of amide alkylation obviously, suggesting the reaction is homogeneous [Scheme 3, Eq.…”

Section: Resultsmentioning

confidence: 69%

“…[17] Initially, the reaction of benzyl alcohol with N,N-dimethylacetamide (3 equiv.) [17] Initially, the reaction of benzyl alcohol with N,N-dimethylacetamide (3 equiv.)…”

Section: Resultsmentioning

confidence: 99%

“…Complexes 1-5 were known complexes and synthesized as previously described by us. [17] Initially, the reaction of benzyl alcohol with N,N-dimethylacetamide (3 equiv.) was chosen as the model reaction, t-BuOK (1.5 equiv.)…”

Section: Resultsmentioning

confidence: 99%

“…Ru complexes 1-5 were prepared as previously described, [17] respectively. Solvents were distilled from appropriate drying agents under Ar before use.…”

Section: Experimental Section General Considerationsmentioning

confidence: 99%

“…Recently, our group has reported several transition metal complexes for borrowing hydrogen reactions, [16] including αalkylation of ketones. [16c-d] As an extension, herein we present a bidentate Ru(II)-NC complex {(C 5 H 4 N)-(C 6 H 4 )}RuCl(CO)(PPh 3 ) 2 (1), which is active for the dehydrogenative reaction from primary alcohols to carboxylic acids, [17] for α-alkylation of unactivated amides and esters with alcohols (Scheme 1). With low catalyst loading (0.5 mol%), complex 1 showed excellent conversions and functional group tolerance under relatively mild conditions (80°C) in short reaction times (6 h for amides and 1.5 h for esters).…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Bidentate Ru(II)‐NC Complexes as Catalysts for α‐Alkylation of Unactivated Amides and Esters

Gong

Yang

et al. 2019

ChemCatChem

Self Cite

View full text Add to dashboard Cite

Five Ru(II)-NC complexes were tested as catalysts for αalkylation of unactivated amides using alcohols as alkylating agents, and complex {(C 5 H 4 N)-(C 6 H 4 )}RuCl(CO)(PPh 3 ) 2 (1) showed the highest activity. With 0.5 mol% catalyst loading, a series of α-alkylated amides were isolated at 80°C within 6 hours.Furthermore, under similar conditions, complex 1 was also active for α-alkylation of unactivated esters with alcohols, and the reaction time was shortened to 1.5 hours. The catalytic performance of 1 is comparable to the best reported catalyst. Reaction of N,N-dimethylcinnamamide with benzyl alcohol:Ruthenium catalyst (0.005 mmol), t-BuOK (1.5 mmol), internal standard (dodecane, 0.5 mmol), benzyl alcohol (1 mmol) and N,Ndimethylcinnamamide (1 mmol) were dissolved in toluene (3 mL) and the solution was heated to 80°C for 6 h under an Ar atmosphere. The yield was calculated by GC using dodecane as the internal standard.

show abstract

Section: Resultsmentioning

confidence: 69%

“…[17] Initially, the reaction of benzyl alcohol with N,N-dimethylacetamide (3 equiv.) [17] Initially, the reaction of benzyl alcohol with N,N-dimethylacetamide (3 equiv.)…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…Ru complexes 1-5 were prepared as previously described, [17] respectively. Solvents were distilled from appropriate drying agents under Ar before use.…”

Section: Experimental Section General Considerationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Bidentate Ru(II)‐NC Complexes as Catalysts for α‐Alkylation of Unactivated Amides and Esters

Gong

Yang

et al. 2019

ChemCatChem

Self Cite

View full text Add to dashboard Cite

show abstract

Bidentate Ru(II)‐NC Complexes as Catalysts for Transfer Hydrogenation of Ketones with Ethanol

Li,

Lian,

Wang

et al. 2024

Asian J Org Chem

Self Cite

View full text Add to dashboard Cite

We developed a bidentate Ru(II)‐NC‐catalyzed transfer hydrogen reaction of ketones using ethanol (EtOH) as the hydrogen source under a weak base condition. The control experiments suggested that the reaction proceeds via the Ru‐H mechanism and yields ethyl acetate as the only byproduct. The deuterium‐labeling experiments further showed that hydrogen evolved from the CH2 and OH groups. The results provide a new weak base system for the transfer hydrogen reaction of ketones using ethanol as the hydrogen donor.

show abstract

Half‐sandwich iridium complexes: Synthesis and catalytic activity in dehydrogenation of alcohols to carboxylic acids

Ye,

Yao

2024

Applied Organom Chemis

View full text Add to dashboard Cite

A series of N,N‐chelate half‐sandwich iridium complexes were synthesized by a simple method with good yields. The dehydrogenation of a series of aromatic and aliphatic primary alcohols to corresponding carboxylic acids has been successfully achieved by the prepared air stable iridium complexes under mild reaction conditions. Carboxylic acids were obtained in high yields under open flask condition with broad substrates and good tolerance to sensitive functional groups. Such a half‐sandwich iridium catalyst system showed desirable stability and catalytic activity, and the achievement of a high TOF of 372.0 h−1 could be observed with an extremely low catalyst loading of only 0.05 mol%. Furthermore, the sustainable catalyst could be reused for a minimum of five cycles without obviously losing its activity, highlighting its potential application in industry. Structure of N,N‐chelate iridium complexes 1 and 3 were determined by single‐crystal X‐ray analysis.

show abstract

Bidentate Ru(ii)-NC complexes as catalysts for the dehydrogenative reaction from primary alcohols to carboxylic acids

Abstract: Complex 1 is active for alcohol dehydrogenative reactions, and two critical intermediates were isolated and characterized.

Cited by 29 publications

References 33 publications

Bidentate Ru(II)‐NC Complexes as Catalysts for α‐Alkylation of Unactivated Amides and Esters

Bidentate Ru(II)‐NC Complexes as Catalysts for α‐Alkylation of Unactivated Amides and Esters

Bidentate Ru(II)‐NC Complexes as Catalysts for Transfer Hydrogenation of Ketones with Ethanol

Half‐sandwich iridium complexes: Synthesis and catalytic activity in dehydrogenation of alcohols to carboxylic acids

Contact Info

Product

Resources

About