Catalytic Addition of C-H Bonds to Multiple Bonds. The First Stage.

Murai, Shinji

doi:10.5059/yukigoseikyokaishi.52.992

Cited by 19 publications

(1 citation statement)

References 8 publications

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“…To attain both high efficiency and high regioselectivity in the cleavage of a C−H bond in a benzene ring, the presence of a directing group 17 at an appropriate position is effective, in order to position the metal close to the C−H bond (Scheme ). Indeed, several functional groups, such as ketones, esters, pyridine, , diazo, and imine have been found to promote C−C bond formation with the regioselective cleavage of C−H bonds. We wish to report that carbonylation at a C−H bond in the benzene ring takes place during the Ru 3 (CO) 12 -catalyzed reaction of pyridylbenzenes with CO and olefins.…”

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Ru₃(CO)₁₂-Catalyzed Reaction of Pyridylbenzenes with Carbon Monoxide and Olefins. Carbonylation at a C−H Bond in the Benzene Ring

et al. 1997

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A ruthenium-catalyzed carbonylation at a C-H bond in a benzene ring is described. The reaction of pyridylbenzenes with CO (20 atm) and ethylene in toluene at 160 degrees C in the presence of a catalytic amount of Ru(3)(CO)(12) results in propionylation at an ortho C-H bond in the benzene ring. Carbonylation does not occur at the pyridine ring, although this is necessary as a directing group to promote the reaction. Olefins such as trimethylvinylsilane and tert-butylethylene in place of ethylene can also be used in this reaction, however 1-hexene, cyclohexene, allyltrimethylsilane, styrene, methyl methacrylate, vinyl acetate, triethoxyvinylsilane, and isopropenyltrimethylsilane do not afford the coupling products. Transition metal complexes, other than ruthenium carbonyl, examined thus far, do not show catalytic activity. In the reaction of meta-substituted pyridylbenzenes, such as those having Me, OMe, CF(3), and COOMe group at the meta position in the benzene ring, carbonylation takes place at the less hindered C-H bond exclusively, irrespective of the electronic nature of the substituents. It is apparent that steric factors are more important for the control of regioselectivity. The reaction is also applicable to naphthyl and thienyl rings. Six-membered heterocycles, such as 2-pyrimidine and 4-pyrimidine, are also effective directing groups for carbonylation at a C-H bond in the benzene ring. The present reaction represents the first, effective catalytic carbonylation reaction involving cleavage of the benzene C-H bond.

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Ru₃(CO)₁₂-Catalyzed Reaction of Pyridylbenzenes with Carbon Monoxide and Olefins. Carbonylation at a C−H Bond in the Benzene Ring

et al. 1997

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Synthetic Applications of Allylsilanes and Vinylsilanes

Luh

Liu

2009

Patai's Chemistry of Functional Groups

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Introduction Electrophilic Substitution of C  Si Bonds Organometallic Reagents Promoted C  Si Cleavage Reactions Miscellaneous C  Si Cleavage Reactions Reactions of Allylsilanes and Vinylsilanes without Cleavage of the C  Si Bond

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Ruthenium‐Catalyzed CH Activation in Target Oriented Synthesis of Natural Products and Active Pharmaceutical Intermediates

Kommagalla¹,

Ramana²

2022

Handbook of CH-Functionalization

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In this article, some of the ruthenium‐catalyzed directed and nondirected CH activation led functionalizations, such as alkylation, alkenylation, arylation, and amidation, which have been elegantly applied in the synthesis of various natural products and active pharmaceutical intermediates (API), has been described. Along with this, the novel approaches like the transient directing group (TDG) and chiral transient directing group (CTDC) aided asymmetric synthesis of the key intermediates employed in a total synthesis have been also narrated. In the majority of the cases, readily available inexpensive and air tolerant [RuCl 2 ( p ‐cymene)] 2 and RuCl 3 · x H 2 O complexes were often employed as catalysts, thus providing the sustainable step economic strategies for natural products and APIs synthesis and as potential alternative to conventional methods.

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Catalytic Addition of C-H Bonds to Multiple Bonds. The First Stage.

Abstract: Some ruthenium complexes have been found to catalyze the direct addition of ortho carbon-hydrogen bonds in aromatic ketones to olefins with high efficiency and selectivity.

Cited by 19 publications

References 8 publications

Ru₃(CO)₁₂-Catalyzed Reaction of Pyridylbenzenes with Carbon Monoxide and Olefins. Carbonylation at a C−H Bond in the Benzene Ring

Ru₃(CO)₁₂-Catalyzed Reaction of Pyridylbenzenes with Carbon Monoxide and Olefins. Carbonylation at a C−H Bond in the Benzene Ring

Synthetic Applications of Allylsilanes and Vinylsilanes

Ruthenium‐Catalyzed CH Activation in Target Oriented Synthesis of Natural Products and Active Pharmaceutical Intermediates

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Catalytic Addition of C-H Bonds to Multiple Bonds. The First Stage.

Abstract: Some ruthenium complexes have been found to catalyze the direct addition of ortho carbon-hydrogen bonds in aromatic ketones to olefins with high efficiency and selectivity.

Cited by 19 publications

References 8 publications

Ru3(CO)12-Catalyzed Reaction of Pyridylbenzenes with Carbon Monoxide and Olefins. Carbonylation at a C−H Bond in the Benzene Ring

Ru3(CO)12-Catalyzed Reaction of Pyridylbenzenes with Carbon Monoxide and Olefins. Carbonylation at a C−H Bond in the Benzene Ring

Synthetic Applications of Allylsilanes and Vinylsilanes

Ruthenium‐Catalyzed CH Activation in Target Oriented Synthesis of Natural Products and Active Pharmaceutical Intermediates

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Product

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Ru₃(CO)₁₂-Catalyzed Reaction of Pyridylbenzenes with Carbon Monoxide and Olefins. Carbonylation at a C−H Bond in the Benzene Ring

Ru₃(CO)₁₂-Catalyzed Reaction of Pyridylbenzenes with Carbon Monoxide and Olefins. Carbonylation at a C−H Bond in the Benzene Ring