Rhodium(I)‐Catalyzed Arylation of β‐Chloro Ketones and Related Derivatives through Domino Dehydrochlorination/ Conjugate Addition

Jiang, Quanbin; Guo, Tenglong; Wang, Qingfu; Wu, Ping; Yu, Zhengkun

doi:10.1002/adsc.201200821

Cited by 26 publications

(18 citation statements)

References 39 publications

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“…1‐(4‐chlorophenyl)‐3‐(3‐methoxyphenyl)propan‐1‐one (3 ed) Yield 222.5 mg 81 % (Catalyst Ru1 ), 241.8 mg 88 % (Catalyst Ru2 ); 1 H NMR (400 MHz, CDCl 3 ) δ 7.87 (d, J =8.6 Hz, 2H), 7.40 (d, J =8.6 Hz, 2H), 7.20 (t, J =7.8 Hz, 1H), 6.84–6.72 (m, 3H), 3.78 (s, 3H), 3.24 (t, J =7.2 Hz, 2H), 3.01 (t, J =8.0 Hz, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ 198.04, 159.83, 142.78, 139.59, 135.21, 129.64, 129.54, 129.00, 120.83, 114.35, 111.51, 55.26, 40.42, 30.15.…”

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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“… White solid, 93% yield. 1 H NMR (400 MHz, 303 K, CDCl 3 ): δ 7.95 (d, J H‐H = 9.2 Hz, 2 H, Ar‐ H ), 7.26 (m, 5 H, Ar‐ H ), 6.93 (d, J H‐H = 8.8 Hz, 2 H, Ar‐ H ), 3.86 (s, 3 H, OC H 3 ), 3.25 (t, J H‐H = 7.2 Hz, 2 H, C H 2 ), 3.06 (t, J H‐H = 8.4 Hz, 2 H, C H 2 ).…”

Section: Methodsmentioning

confidence: 99%

Piano‐stool Ru (II) arene complexes that contain ethylenediamine and application in alpha‐alkylation reaction of ketones with alcohols

Kavukcu

Günnaz

Şahın

et al. 2019

Applied Organom Chemis

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A series of piano‐stool Ru (II) complexes (Ru1–7) bearing ethylenediamine with aryl and aliphatic groups were prepared and fully characterized by 1H, 13C, 19F and 31P NMR spectroscopy, FT‐IR and elemental analysis. The crystal structures of Ru2–4 and Ru7 were determined by X‐ray crystallography. They were successfully applied to the alpha(α)‐alkylation of aliphatic and aromatic ketones with alcohols via the borrowing hydrogen strategy in mild reaction conditions within a short time. The catalytic system has a broad substrate scope, which allows the synthesis of alpha alkylated ketones with excellent yields. The electronic and steric effects of complexes on catalytic activity were analysed. The influence of the carbon chain length of the ligand on the alpha‐alkylation reaction of ketones was also investigated. The catalytic cycle was also examined by 1H‐NMR spectroscopy in d8‐toluene.

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“…Yield: 256.4 mg, 89 %, mp 69-70°C. 1 3-Naphthalen-1-yl-1-phenyl-propan-1-one (3 qa): [27] Colorless oil. Yield: 234.1 mg, 91 %.…”

Section: General Procedures For Catalytic Cyclementioning

confidence: 99%

Iridium Complexes as Efficient Catalysts for Construction of α‐Substituted Ketones via Hydrogen Borrowing of Alcohols in Water

et al. 2021

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Ketones are of great importance in synthesis, biology, and pharmaceuticals. This paper reports an iridium complexes‐catalyzed cross‐coupling of alcohols via hydrogen borrowing, affording a series of α‐alkylated ketones in high yield (86 %–95 %) and chemoselectivities (>99 : 1). This methodology has the advantages of low catalyst loading (0.1 mol%) and environmentally benign water as the solvent. Studies have shown the amount of base has a great impact on chemoselectivities. Meanwhile, deuteration experiments show water plays an important role in accelerating the reduction of the unsaturated ketones intermediates. Remarkably, a gram‐scale experiment demonstrates this methodology of iridium‐catalyzed cross‐coupling of alcohols has potential application in the practical synthesis of α‐alkylated ketones.

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Rhodium(I)‐Catalyzed Arylation of β‐Chloro Ketones and Related Derivatives through Domino Dehydrochlorination/ Conjugate Addition

Cited by 26 publications

References 39 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

Piano‐stool Ru (II) arene complexes that contain ethylenediamine and application in alpha‐alkylation reaction of ketones with alcohols

Iridium Complexes as Efficient Catalysts for Construction of α‐Substituted Ketones via Hydrogen Borrowing of Alcohols in Water

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