28049-67-4

Upstream product

• 140-29-4 phenylacetonitrile 
• 106-95-6 allyl bromide 
• 107-05-1 3-chloroprop-1-ene 
• 92954-34-2 2-allyl-1,3-dicyclohexylisourea 
• 107-18-6 allyl alcohol 
• 5558-87-2 2-phenylpent-4-enenitrile 
• 66205-43-4 cyano-allyl-phenyl-acetic acid ethyl ester 
• 1331858-85-5 C₁₅H₁₇NO₂ 
• 1331858-75-3 C₁₃H₁₃NO 
• 591-87-7 Allyl acetate 
• 100-47-0 benzonitrile 

Downstream Products

• 3563-57-3 2-allyl-2-phenyl-pent-4-enoic acid amide 
• 171858-58-5 2-Phenyl-2-(2-propenyl)-4-pentenecarboxaldehyde 
• 158943-16-9 1-phenylcyclopent-3-enecarbonitrile 
• 13065-76-4 2-allyl-2-phenylpent-4-en-1-amine 

Relevant academic research and scientific papers

Surprising and Highly Efficient Use of Methylmagnesium Chloride as a Non-Nucleophilic Base in the Deprotonation and Alkylation of sp3 Centres Adjacent to Nitriles

Methylmagnesium chloride (MeMgCl) is a key reagent in research and industry typically as a nucleophile. In this article we develop the use of MeMgCl as a non-nucleophilic base in conjunction with catalytic amounts of an amine mediator. Specifically, we use the base to deprotonate α to a variety of nitriles in alkylation reactions, applying it to the synthesis of a wide variety of tertiary and quaternary nitriles, including examples where we successively and successfully added three different substituents on the carbon α to the nitrile. This method is generally applicable, high yielding and much greener than existing methods, and it has considerable advantages for industrial application.

Alkylation and hydrolysis of phenylacetonitriles under microwave irradiation

Alkylation of phenylacetonitriles is performed by solid-liquid phase transfer catalysis in 1-3 minutes under microwave irradiation (one hour with a two-phase system). These nitriles can be quickly hydrolysed in a microwave oven to yield the corresponding amides or acids according to the reaction time.

Efficient and Clean Nickel Catalyzed α-Allylation Reaction of Nitriles

A clean method has been developed for the α-allylation of phenyl and alpha alkyl phenyl acetonitrile with allylic alcohols. The reaction is catalyzed by nickel complexes in situ generated from a combination of Ni(cod)2 and the dppf ligand and performed at 80 °C in methanol as reaction solvent.Accordingly to this simple and base-free protocol that only yields water as a side-product, many allylic nitriles were synthetized with good yields. (Figure presented.).

Pd-Catalyzed Rearrangement of N-Alloc- N-allyl Ynamides via Auto-Tandem Catalysis: Evidence for Reversible C-N Activation and Pd(0)-Accelerated Ketenimine Aza-Claisen Rearrangement

An auto-tandem catalytic double allylic rearrangement of N-alloc-N-allyl ynamides was developed. This reaction proceeds through two separate and distinct catalytic cycles with both decarboxylative Pd-π-allyl and Pd(0)-promoted aza-Claisen rearrangements occurring. A detailed mechanistic study supported by computations highlights these two separate mechanisms. Previously unreported reversible C-N ionization and a Pd(0)-catalyzed [3,3]-sigmatropic rearrangement were discovered. This study provides new reaction pathways for both π-allyl and sigmatropic rearrangements.

Enantioselective Palladium-Catalyzed Oxidative Cascade Cyclization of Aliphatic Alkenyl Amides

The catalyst system of Pd(TFA)2/(S,S)-diPh-pyrox is reported to promote the highly efficient enantioselective oxidative cascade cyclization of alkene-tethered aliphatic acrylamides under mild aerobic conditions. A series of pyrrolizidine derivatives have been synthesized in good yield and excellent enantioselectivity. Deuterium-labeling experiments have revealed that the reaction proceeded through an anti-aminopalladation (anti-AP) pathway with high selectivity. The transition states for the anti-AP step have been calculated to account for the observed enantioselectivity.

Highly enantioselective hydroamination to six-membered rings by heterobimetallic catalysts

New bimetallic Zn/Zr salen-type systems were employed as catalysts in the asymmetric intramolecular hydroamination reaction. High enantioselectivity for the formation of piperidines of up to 98% ee were observed. This journal is the Partner Organisations

6-azabicyclo[3.2.1]octanes via copper-catalyzed enantioselective alkene carboamination

Bridged bicyclic rings containing nitrogen heterocycles are important motifs in bioactive small organic molecules. An enantioselective copper-catalyzed alkene carboamination reaction that creates bridged heterocycles is reported herein. Two new rings are

Cu(II)-mediated aminooxygenation of alkenylimines and alkenylamidines with TEMPO

A method for the synthesis of oxymethyl dihydropyrroles (pyrrolines) and dihydroimidazoles has been developed via Cu(II)-mediated intramolecular aminooxygenation of alkenylimines and alkenylamidines, respectively, with 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO). Georg Thieme Verlag Stuttgart · New York.

Deacylative allylation: Allylic alkylation via retro-Claisen activation

A new method for allylic alkylation of a variety of relatively nonstabilized carbon nucleophiles is described herein. In this process of "deacylative allylation", the coupling partners, an allylic alcohol and a ketone pronucleophile, undergo in situ retro-Claisen activation to generate an allylic acetate and a carbanion. In the presence of palladium, these reactive intermediates undergo catalytic coupling to form a new C-C bond. In comparison to unimolecular decarboxylative allylation, a commonly utilized method for allylation of carbon anions, deacylative allylation is an intermolecular process. Moreover, deacylative allylation allows the direct coupling of readily available allylic alcohols. Lastly, the full utility of deacylative allylation is demonstrated by the rapid construction of a variety 1,6-heptadienes via 3-component couplings.

Reverse Cope Elimination Reactions. 2. Application to Synthesis

Intramolecular addition of N,N-disubstituted hydroxylamines to unactivated olefins was used to prepare an indolizine, a pyrroloisoquinoline, a 1,8-diazaspirodecane, a cyclopentapyrrole, and an isoindoline.A pyrrolizine and a 1-azabicyclo2.