114475-19-3

Upstream product

• 504-85-8 4-methyl-pent-3-enoic acid 
• 62-53-3 aniline 
• 79-91-4 terebic acid 
• 4786-23-6 4-methyl-3-pentenenitrile 
• 201230-82-2 carbon monoxide 
• 503-60-6 3,3-dimethyl-allyl chloride 
• 78-79-5 isoprene 
• 556-82-1 3-methyl-2-buten-1-ol 
• 41199-96-6 4-methyl-3-pentenoic acid chloride 
• 103-71-9 phenyl isocyanate 

Downstream Products

• 212504-72-8 2-(3,3-Dimethyl-oxiranyl)-N-phenyl-acetamide 
• 1016225-18-5 3-hydroxy-4-methyl-N-phenylpentanamide 
• 4685-97-6 4-hydroxy-4-methyl-valeric acid anilide 

Relevant academic research and scientific papers

Palladium-Catalyzed Aminocarbonylation of Allylic Alcohols

A benign and efficient palladium-catalyzed aminocarbonylation reaction of allylic alcohols is presented. The generality of this novel process is demonstrated by the synthesis of β,γ-unsaturated amides including aliphatic, cinnamyl, and terpene derivatives. The choice of ligand is crucial for optimal carbonylation processes: Whereas in most cases the combination of PdCl2with Xantphos (L6) gave best results, sterically hindered substrates performed better in the presence of simple triphenylphosphine (L10), and primary anilines gave the best results using cataCXium PCy (L8). The reactivity of the respective catalyst system is significantly enhanced by addition of small amounts of water. Mechanistic studies and control experiments revealed a tandem allylic alcohol amination/C?N bond carbonylation reaction sequence.

Selective palladium-catalyzed aminocarbonylation of 1,3-dienes: Atom-efficient synthesis of β,γ-unsaturated amides

Carbonylation reactions constitute important methodologies for the synthesis of all kinds of carboxylic acid derivatives. The development of novel and efficient catalysts for these transformations is of interest for both academic and industrial research. Here, the first palladium-based catalyst system for the aminocarbonylation of 1,3-dienes is described. This atom-efficient transformation proceeds under additive-free conditions and provides straightforward access to a variety of β,γ-unsaturated amides in good to excellent yields, often with high selectivities.

One-pot amide synthesis from allyl or benzyl halides and amines by Pd-catalysed carbonylation

Amides can be prepared from allyl or benzyl halides and primary or secondary amines, using Pd(0) catalyst under CO pressure, in a one-pot synthesis. The reaction proceeds through the acyl palladium halide formation which undergoes an acylic nucleophilic substitution from the amine.

Efficient amide-directed catalytic asymmetric hydroboration

A series of acyclic β,γ-unsaturated amides are shown to undergo highly regio- (>95%) and enantioselective (93-99% ee) rhodium-catalyzed hydroboration with pinacolborane (PinBH) using simple chiral monophosphite or phosphoramidite ligands in combination wi

Synthesis of γ-hydroxy α,β-unsaturated amides by base induced isomerization of epoxy amides

Treatment of 3,4-epoxyamides with LDA affords γ-hydroxy-α,β- unsaturated amides, usually with high (E)-selectivity. The 3,4-epoxyamides were prepared by the epoxidation of β,γ-unsaturated amides with meta- chloroperbenzoic acid.

STOECHIOMETRISCHE UND KATALYTISCHE CC-VERKNUEPFUNGEN ZWISCHEN 1,3-BUTADIEN UND PHENYLISOCYANAT AN NICKEL(0)-KOMPLEXEN

The CC coupling of 1,3-butadiene with phenylisocyanate at nickel(0) systems is ligand-dependent.Basic phosphanes such as triethyl- or tricyclohexylphosphane induce a stoichiometric 1/1 CC-coupling reaction yielding azanickela complexes.Triphenylphosphane, on the other hand, leads to a catalytic reaction.Catalysis is initiated by 2/1 coupling, which, after intramolecular cyclisation finally yields carbocyclic five-ring amides.Some special features are listed and the reaction mechanisms are discussed.