Study on the Pd/C‐Catalyzed (Retro‐)Michael Addition Reaction of Activated Methylene Compounds to Electron‐Poor Styrenes

Nikishkin, Nicolai I.; Huskens, Jurriaan; Verboom, Willem

doi:10.1002/ejoc.201000961

Cited by 19 publications

(7 citation statements)

References 21 publications

(16 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Reports of Pd/C-catalyzed C–H activations, − while still relatively uncommon, have become more prevalent in recent years, as palladium on carbon is being applied to transformations previously reserved for more complicated homogeneous catalytic systems. − Among these, direct arylations remain limited − and are rarely reported for non-heteroaromatic systems . The formation of a significant proportion of 12a from the reaction of 3 and 9a under simple conditions therefore presented an interesting side-reaction worth investigating further (Table ).…”

Section: Resultsmentioning

confidence: 99%

What Is the Structure of the Antitubercular Natural Product Eucapsitrione?

et al. 2017

View full text Add to dashboard Cite

1,5,7-Trihydroxy-6H-indeno[1,2-b]anthracene-6,11,13-trione (1), proposed to be the antitubercular natural product eucapsitrione, has been synthesized in 43% overall yield and six steps, including a key Suzuki-Miyaura biaryl coupling and a directed remote metalation (DReM)-initiated cyclization. The physical and spectroscopic properties of 1 do not match the data reported for the natural product. At this time there is insufficient information available to enable a structure reassignment. During the optimization of the Suzuki-Miyaura coupling, an unprecedented biaryl coupling ortho to the borono group was observed. The scope of this unusual reaction has been investigated.

show abstract

Section: Resultsmentioning

confidence: 99%

What Is the Structure of the Antitubercular Natural Product Eucapsitrione?

et al. 2017

View full text Add to dashboard Cite

show abstract

“…In 2010 Verboom and co‐workers revealed a simple Pd/C‐catalyzed Michael addition of activated methylene compounds to electron‐poor styrenes. They found that the Pd/C catalyst is very robust, air‐stable, and easily removed . In 2014 Pihko and co‐workers established that use of activated Pd/C as catalyst for the chemo‐ and stereoselective hydrosilylation of α,β‐unsaturated carbonyl compounds in the presence of 1.1 equiv.…”

Section: Applications Of Pd/cmentioning

confidence: 99%

Development of the Applications of Palladium on Charcoal in Organic Synthesis

Liu

Astruc

2018

Adv Synth Catal

View full text Add to dashboard Cite

Palladium on charcoal( Pd/C)h as lots of salient merits:( i) it is ac heap andc ommercial source of palladium, (ii)i ts hows efficientc atalytic activity even without ligands,( iii)a saheterogeneous catalyst it is easily recycledm any times by simple filtration,a nd (iv) it is applicablet oag reat number of reactions and substrates,a lthough it is eventually less efficient than homogeneous Pd catalysts containing some sophisticated ligands.T hisr eview recalls the main background ands ummarizes the progress made essentially during the last twelve years in Pd/C-catalyzed organic synthesis since the reviews by Felpins group andSekiin2 006.

show abstract

“…The reaction was carried out by refluxing the starting compounds in methanol for 2–12 h. We hypothesized that the formation of tetrahydropyridine occurs through the following sequence of reactions: Michael addition to obtain 2-substituted 3-aryl-4,4-dicyanobutanoic acid ester A , Mannich reaction to give 2-substituted 5-amino-3,5-diaryl-4,4-dicyanopentanoic acid B , intramolecular cyclization yielding polysubstituted 2-hydroxypiperidine C , and dehydration ( Scheme 1 ). Previously, Verboom et al [ 48 ] studied the formation of close analogues of intermediate A from benzylidenemalononitriles and malononitrile, or ethyl cyanoacetate. However, the intermediates B and C have never been isolated or identified.…”

Section: Introductionmentioning

confidence: 99%

Tetrahydropyridines’ Stereoselective Formation, How Lockdown Assisted in the Identification of the Features of Its Mechanism

Vereshchagin¹,

Iliyasov²,

Karpenko³

et al. 2022

Molecules

View full text Add to dashboard Cite

The multicomponent reaction of aldehydes, cyano-containing C-H acids, esters of 3-oxocarboxylic acid and ammonium acetate led to unexpected results. The boiling of starting materials in methanol for one to two hours resulted in the formation of polysubstituted 1,4,5,6-tetrahydropyridines with two or three stereogenic centers. During the 2020 lockdown, we obtained key intermediates of this six-step domino reaction. A number of fast and slow reactions occurred during the prolonged stirring of the reaction mass at rt. Sequence: 1. Knoevenagel condensation; 2. Michael addition; 3. Mannich reaction; 4. cyclization—fast reactions and cyclization of the product polysubstituted 2-hydroxypiperidine—was isolated after 40 min stirring at rt. Further monitoring proved the slow dehydration of 2-hydroxypiperidine to obtain 3,4,5,6-tetrahydropyridine after 7 days. Then, four-month isomerization occurred with 1,4,5,6-tetrahydropyridine formation. All reactions were stereoselective. Key intermediates and products structures were verified by X-ray diffraction analysis. Additionally, we specified conditions for the selective intermediates’ preparation.

show abstract

Study on the Pd/C‐Catalyzed (Retro‐)Michael Addition Reaction of Activated Methylene Compounds to Electron‐Poor Styrenes

Cited by 19 publications

References 21 publications

What Is the Structure of the Antitubercular Natural Product Eucapsitrione?

What Is the Structure of the Antitubercular Natural Product Eucapsitrione?

Development of the Applications of Palladium on Charcoal in Organic Synthesis

Tetrahydropyridines’ Stereoselective Formation, How Lockdown Assisted in the Identification of the Features of Its Mechanism

Contact Info

Product

Resources

About