Ligand Control of Palladium‐Catalyzed Site‐Selective α‐ and γ‐Arylation of α,β‐Unsaturated Ketones with (Hetero)aryl Halides

2020 ◽  
Vol 59 (52) ◽  
pp. 23438-23444
Author(s):  
On Ying Yuen ◽  
Chau Ming So
Keyword(s):  
Aryl Halides ◽  
Unsaturated Ketones ◽  
Palladium Catalyzed ◽  
Site Selective

Palladium-Catalyzed Ring-Opening Coupling of Cyclobutenols with Aryl Halides

Synlett ◽  
2017 ◽  
Vol 29 (06) ◽  
pp. 754-758 ◽  
Author(s):  
Takanori Matsuda ◽  
Takeshi Matsumoto ◽  
Akira Murakami
Keyword(s):  
Aromatic Compounds ◽  
Ring Opening ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Aryl Halides ◽  
Ortho Position ◽  
Unsaturated Ketones ◽  
Cross Coupling Reaction ◽  
Palladium Catalyzed ◽  
Intramolecular Condensation

A palladium(0)-catalyzed ring-opening cross-coupling reaction between tert-cyclobutenols and aryl halides produces γ-arylated β,γ-unsaturated ketones. In the case of aryl halides bearing functional groups at the ortho position, the resulting ring-opened ketones undergo intramolecular condensation to afford bicyclic aromatic compounds.

Palladium-Catalyzed Synthesis of β,β-Diaryl α,β-Unsaturated Ketones

Synthesis ◽  
2018 ◽  
Vol 51 (06) ◽  
pp. 1455-1465 ◽  
Author(s):  
Li-ming Shao ◽  
Yi-lin Zheng ◽  
Li Xiao ◽  
Qiong Xie
Keyword(s):  
Cross Coupling ◽  
Aryl Halides ◽  
One Pot ◽  
Unsaturated Ketones ◽  
Palladium Catalyzed ◽  
Plausible Mechanism

We herein describe a versatile palladium-catalyzed synthesis of β,β-diaryl α,β-unsaturated ketones. A broad range of aryl halides react with β-arylbutanones to afford biologically useful, symmetrical and unsymmetrical ketones. The use of 4,5-diazafluoren-9-one and oxygen makes this one-pot reaction more applicable. A plausible mechanism involving palladium-catalyzed oxidative Heck-type cross-coupling is also proposed.

Theoretical and experimental studies of palladium-catalyzed site-selective C(sp3)−H bond functionalization enabled by transient ligands

2017 ◽  
Author(s):  
Haibo Ge ◽  
Lei Pan ◽  
Piaoping Tang ◽  
Ke Yang ◽  
Mian Wang ◽  
...  
Keyword(s):  
Bond Activation ◽  
Theoretical Calculations ◽  
Experimental Studies ◽  
Bond Functionalization ◽  
Aliphatic Ketones ◽  
Site Selectivity ◽  
Mechanistic Investigation ◽  
Palladium Catalyzed ◽  
Metal Catalyzed ◽  
Site Selective

Transition metal-catalyzed selective C–H bond functionalization enabled by transient ligands has become an extremely attractive topic due to its economical and greener characteristics. However, catalytic pathways of this reaction process on unactivated sp<sup>3</sup> carbons of reactants have not been well studied yet. Herein, detailed mechanistic investigation on Pd-catalyzed C(sp<sup>3</sup>)–H bond activation with amino acids as transient ligands has been systematically conducted. The theoretical calculations showed that higher angle distortion of C(sp2)-H bond over C(sp3)-H bond and stronger nucleophilicity of benzylic anion over its aromatic counterpart, leading to higher reactivity of corresponding C(sp<sup>3</sup>)–H bonds; the angle strain of the directing rings of key intermediates determines the site-selectivity of aliphatic ketone substrates; replacement of glycine with β-alanine as the transient ligand can decrease the angle tension of the directing rings. Synthetic experiments have confirmed that β-alanine is indeed a more efficient transient ligand for arylation of β-secondary carbons of linear aliphatic ketones than its glycine counterpart.<br><br>

Palladium Catalyzed Cascade Azidation/Carbonylation of Aryl Halides with Sodium Azide for the Synthesis of Amides

2021 ◽  
Author(s):  
Zhuang Qi ◽  
Shan‐Shan Li ◽  
Lin Li ◽  
Qi Qin ◽  
Li‐Miao Yang ◽  
...  
Keyword(s):  
Sodium Azide ◽  
Aryl Halides ◽  
Palladium Catalyzed
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