BINAP-copper supported by hydrotalcite as an efficient catalyst for the borrowing hydrogen reaction and dehydrogenation cyclization under water or solvent-free conditions

Xu, Zhaojun; Yu, Xinyan; Sang, Xinxin; Wang, Dawei

doi:10.1039/c8gc00557e

Cited by 111 publications

(38 citation statements)

References 68 publications

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“…1‐(4‐bromophenyl)‐3‐(4‐chlorophenyl)propan‐1‐one (3 be) Yield 294.5 mg 91 % (Catalyst Ru1 ), 300.9 mg 93 % (Catalyst Ru2 ); 1 H NMR (400 MHz, CDCl 3 ) δ 7.78 (d, J =8.6 Hz, 2H), 7.57 (d, J =8.6 Hz, 2H), 7.24 (d, J =8.4 Hz, 2H), 7.15 (d, J =8.4 Hz, 2H), 3.22 (t, J =7.5 Hz, 2H), 3.01 (t, J =7.5 Hz, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ 197.90, 139.55, 135.50, 129.89, 129.61, 128.73, 128.46, 40.20, 29.33.…”

Section: Methodsmentioning

confidence: 99%

Efficient Organoruthenium Catalysts for α‐Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies

Maji

Singh

et al. 2020

ChemCatChem

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A new family of phosphine free organometallic ruthenium(II) catalysts (Ru1–Ru4) supported by bidentate NN Schiff base ligands (L1–L4 where L1=N,N‐dimethyl‐4‐((2‐phenyl‐2‐(pyridin‐2‐ylmethyl)hydrazineylidene)methyl) aniline, L2=N,N‐diethyl‐4‐((2‐phenyl‐2‐(pyridin‐2‐ylmethyl)hydrazineylidene)methyl)aniline, L3=N,N‐dimethyl‐4‐((2‐phenyl‐2‐(pyridin‐2‐yl)hydrazineylidene)methyl)‐ aniline and L4=N,N‐diethyl‐4‐((2‐phenyl‐2‐(pyridin‐2‐yl)hydrazineylidene)methyl) aniline) was prepared and characterized. These half‐sandwich complexes acted as catalysts for C−C bond formation and exhibited excellent performance in the dehydrogenative coupling of ketones and amides. In the synthesis of C–C bonds, alcohols were utilized as the alkylating agent. A broad range of substrates, including sterically hindered ketones and alcohols, were well tolerated under the optimized conditions (TON up to 47000 and TOF up to 11750 h−1). This ruthenium (II) catalysts were also active towards the dehydrogenative cyclization of o‐amino benzyl alcohol for the formation of quinolines derivatives. Various polysubstituted quinolines were synthesized in moderate to excellent yields (TON up to 71000 and TOF up to 11830 h−1). Control experiments were carried out and the ruthenium hydride intermediate was characterized to support the reaction mechanism and a probable reaction pathway of dehydrogenative coupling for the C−C bond formation has been proposed.

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Section: Methodsmentioning

confidence: 99%

Efficient Organoruthenium Catalysts for α‐Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies

Maji

Singh

et al. 2020

ChemCatChem

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“…[Cu(binap)I] 2 ( 1a ) was synthesized from BINAP and CuI in acetonitrile according to methods in the known literature . Then, [Cu(binap)I] 2 @HT ( 2 ) was prepared through our own method . With this heterogeneous Cu catalyst in hand, [Cu(binap)I] 2 @HT was used to catalyze the C—H hydroxylation of benzenethiol ( 3a ) and phenylboronic acid ( 4a ), and it was found that the desired product ( 5a ) could be obtained smoothly with moderate yield.…”

Section: Resultsmentioning

confidence: 99%

“…Next, the heterogeneous [Cu(binap)I] 2 @HT ( 2a ) were prepared according to our recent method . Hydrotalcite (HT, 1.0 g) was dispersed in dimethyl sulfoxide (DMSO) (20 mL) by ultrasonic method (60 °C, 15 min, three times), and then was introduced to a 100imL Schlenk tube.…”

Section: Methodsmentioning

confidence: 99%

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

Zhang

Wang

et al. 2020

J of Chemical Tech & Biotech

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BACKGROUND Aromatic thioether derivatives exist widely in natural products and have significant applications in modern synthesis and the pharmaceutical industry; for example, 2‐sulfanylphenols and arylthioquinones are important intermediates in the processing of anticancer, antibiotic, antivirus and antimalarial drugs. Direct C─H hydroxylation was considered as one of the efficient methods for the synthesis of these compounds. Homogeneous transition metal catalysts usually were used through a cross‐coupling of halogen‐substituted phenols with thiophenols. However, from the perspectives of sustainable development and easy recovery, it is necessary to develop an efficient and recoverable catalytic system to realize the synthesis of aromatic thioether derivatives with good efficiency and recyclability. RESULTS The heterogeneous catalyst [Cu(binap)I]2@HT in the present work showed good catalytic activity for the C─H hydroxylation of benzenethiol and phenylboronic acid. The catalytic system was tolerant to various substituents including alkyl, alkoxy, ester, halogen or trifluoromethyl on the phenyl ring of the thiophenols or arylboric acids. In addition to electron‐donating groups, the products with strong electron‐withdrawing groups, such as methyl formylate and trifluoromethyl also were achieved with good yields at 90 °C for 12 h (68% and 66%, respectively). Repeated experiment results showed that the catalyst could be reused at least five times without obvious decrease in catalytic activity. CONCLUSION A BINAP‐Cu complex supported on hydrotalcite was prepared and used as a heterogeneous catalyst for the C─H activation of thiophenol under mild reaction conditions. Through a cascade C─H hydroxylation and further oxidation process, 2‐Sulfanylphenols and arylthioquinones could be obtained with moderate‐to‐good yields for a series of 2‐(phenylthio)phenol derivatives using the heterogeneous catalyst [Cu(binap)I]2@HT. In addition, this heterogeneous catalyst showed good recylbility. © 2020 Society of Chemical Industry

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“…The use of magnetic Fe 3 O 4 as catalyst also did not result into the formation of the desired product 3aa (Table , entry 2). A literature survey suggests that nickel based catalyst has been employed for the activation of molecular hydrogen to generate nickel hydride and copper as a potential catalyst for borrowing‐hydrogen reactions . Keeping this thing in mind, NiFe 2 O 4 and CuFe 2 O 4 were employed as a catalyst for this reaction.…”

Section: Resultsmentioning

confidence: 99%

CuNiFe a Magnetic Nano‐Catalyst: an Efficient Catalyst for the Selective Synthesis of Benzoxazoles

Chaurasia

Bhanage

2018

ChemistrySelect

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An efficient protocol for the synthesis of benzoxazoles from o‐nitrophenols and benzyl alcohols using CuNiFe as a magnetic nano‐catalyst via hydrogenation transfer has been described. The CuNiFe magnetic nano‐catalyst was prepared by an operationally simple method, without the use of any toxic reagents. The prepared catalyst was characterized by XRD, FEG‐SEM, EDAX, TEM, and FT‐IR techniques. No additional additives such as oxidants and reductants were required for this reaction. CuNiFe magnetic nano‐catalyst showed good air stability and could be recycled up to six times without any significant loss in its catalytic activity.

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BINAP-copper supported by hydrotalcite as an efficient catalyst for the borrowing hydrogen reaction and dehydrogenation cyclization under water or solvent-free conditions

Abstract: A BINAP-Cu system supported by hydrotalcite has been developed and proved to be a highly efficient catalyst for the atom-efficient and green borrowing hydrogen reaction and dehydrogenative cyclization.

Cited by 111 publications

References 68 publications

Efficient Organoruthenium Catalysts for α‐Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies

Efficient Organoruthenium Catalysts for α‐Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies

The Cascade C─H functionalization with sequential hydroxylation and oxidation through heterogeneous BINAP‐copper on hydrotalcite

CuNiFe a Magnetic Nano‐Catalyst: an Efficient Catalyst for the Selective Synthesis of Benzoxazoles

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