59874-90-7

Upstream product

• 59874-81-6 1-(1-imino-2,2,2-trichloroethoxy)-3-phenyl-2(E)-propene 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 545-06-2 trichloroacetonitrile 
• 104-54-1 3-Phenylpropenol 

Downstream Products

• 136755-31-2 erythro-3-chloro-5-(α-trichloroacetamido)benzyl-2-isoxazoline 
• 136755-31-2 threo-3-chloro-5-(α-trichloroacetamido)benzyl-2-isoxazoline 
• 4393-21-9 1-(phenyl)allylamine 
• 93697-25-7 phenyl-(2,2,2-trichloro-acetylamino)-acetic acid 
• 138816-23-6 (4S,5S)-3,3-Dichloro-4-chloromethyl-5-phenyl-pyrrolidin-2-one 
• 162089-51-2 1-Benzyl-3-(1-phenyl-allyl)-urea 
• 1181394-16-0 1-phenylprop-2-en-1-amine hydrochloride 
• 3558-69-8 2,6-diphenylpyridine 
• 1186139-01-4 (S)-N-(1-phenylallyl)-3,5-dinitrobenzamide 
• 154614-38-7 (+/-)-N-1-acetyl-1-phenyl-2-propenylamine 
• 244092-75-9 (1S)-1-phenyl-2-propen-1-amine 
• 98-83-9 isopropenylbenzene 
• 374725-03-8 tert-butyl (-formyl-1-phenylethyl)carbamate 

Relevant academic research and scientific papers

Novel catalysts for the overman rearrangement

PtCl2, PtCl4, AuCl, and AuCl3 were found to be efficient catalysts for the Overman rearrangement of O- allyltrichloroacetimidates to N-allyltrichloroacetamides. Georg Thieme Verlag Stuttgart.

Determination of the Absolute Configuration of (S)-N-(1-Aryl-allyl)-3,5-dinitrobenzamides and Their Elution Order on Brush-Type Chiral Stationary Phases

A series of ten enantiomerically pure (S)-N-(1-aryl-allyl)-3,5-dinitrobenzamides (S-DNBs) was prepared using enzymatic resolution and chiral chromatography. Enzymatic resolution of corresponding 1-aryl-allylamines using Candida antarctica lipase B (CaLB) was efficient for amines with no steric hindrance near the stereogenic center and S-DNB amides were prepared by acylation of the obtained S-amine. When steric effects interrupted enzymatic resolution, racemic DNB amides were resolved using a brush-type chiral column (CSP-A) developed in our laboratory. Previously reported behavior of CaLB in kinetic resolution of amines was considered a starting point for the determination of absolute configuration (AC). The AC of prepared S-DNB amides was anticipated using the elution order of prepared DNB amides on CSP-A and commercial Whelk-O1 columns and comparison with DNB amides obtained after acylation of (S)-amines. The comparison between experimental electronic circular dichroism (ECD) spectra with those obtained by conformational analysis and ECD calculations of representative compounds allowed us to verify the AC of prepared DNB amides.

A short synthesis of pyridines from deprotonated α-aminonitriles by an alkylation/RCM sequence

α-Aminonitriles can serve as versatile key precursors for the synthesis of nitrogen containing heterocycles. After unsuccessful trials involving the [1,2]-Stevens rearrangement of nitrile-stabilized ammonium ylides, we herein report a simple three-step synthesis of substituted pyridines based on an alkylation/ring-closing metathesis/aromatization sequence.

Palladium-catalyzed anti-markovnikov oxidation of allylic amides to protected β-amino aldehydes

A general method for the preparation of N-protected β-amino aldehydes from allylic amines or linear allylic alcohols is described. Here the Pd(II)-catalyzed oxidation of N-protected allylic amines with benzoquinone is achieved in tBuOH under ambient conditions with excellent selectivity toward the anti-Markovnikov aldehyde products and full retention of configuration at the allylic carbon. The method shows a wide substrate scope and is tolerant of a range of protecting groups. Furthermore, β-amino aldehydes can be obtained directly from protected allylic alcohols via palladium-catalyzed autotandem reactions, and the application of this method to the synthesis of β-peptide aldehydes is described. From a mechanistic perspective, we demonstrate that tBuOH acts as a nucleophile in the reaction and that the initially formed tert-butyl ether undergoes spontaneous loss of isobutene to yield the aldehyde product. Furthermore, tBuOH can be used stoichiometrically, thereby broadening the solvent scope of the reaction. Primary and secondary alcohols do not undergo elimination, allowing the isolation of acetals, which subsequently can be hydrolyzed to their corresponding aldehyde products.

Multifaceted catalysis approach to nitrile activation: Direct synthesis of halogenated allyl amides from allylic alcohols

Allyl amides were synthesised from the reaction of allyl alcohols and halogenated nitriles using a platinum multifaceted catalysis approach in which both the nucleophilic addition and subsequent [3,3]-sigmatropic rearrangement steps of the process were catalysed by the same complex. Additionally, 1H/13C{1H} NMR and GC studies provided the first insights into the mechanism of this transformation.

An efficient enzymatic approach to (S)-1-aryl-allylamines

A range of 1-aryl-allylamines were prepared in moderate to excellent enantioselectivity (ee 63.5%→99.9%) using lipase B from a Candida antarctica catalyzed resolution of racemic amines. This is the first time that CaLB has been used for the resolution of 1-aryl-allylamines. Racemic amines were prepared starting from aromatic aldehydes with a [3,3]-sigmatropic rearrangement of the acyclic imidates as the key step followed by trichloroacetamidate hydrolysis. Aldehydes were converted into acrylic esters using Knoevenagel reaction. After reduction, the corresponding alcohols were used for the preparation of trichloroacetimidates, which were then used in an Overman rearrangement.

Effect of halogenation reagents on halocyclization and Overman rearrangement of allylic trichloroacetimidates

Electrophilic halogen can promote either halocyclization or Overman rearrangement of allylic trichloroacetimidates. We found that the chemoselectivity was dependent on the nature of the halogenation reagents for primary allylic trichloroacetimidates. A one-pot procedure was developed for the preparation of allylic trichloroacetamides directly from allylic alcohols at room temperature.

NEW CHIRAL STATIONARY PHASES FOR CHROMATOGRAPHY BASED ON AROMATIC ALLYL AMINES

New chiral stationary phases (CSPs) based on chiral selectors covalently bound on a solid support were prepared. Chiral selectors were obtained from enantiomerically pure aromatic amines and 3,5-dinitrobenzoic acid and then linked to the support surface through the allylic double bond. Such obtained materials allow enantioseparation of racemates or enantiomerically enriched compounds. These chiral stationary phases can be used as fillings in chromatographic columns for enantiomer separation of naproxen type drugs and other similar non-steroidal anti-inflammatory drugs (NSAID) by means of high performance liquid chromatography on both the analytical and preparative scale.

An investigation into the allylic imidate rearrangement of trichloroacetimidates catalysed by cobalt oxazoline palladacycles

Dimeric palladacycles, di-μX-bis[({η5-(S)-( pR)-2-[2′-(4′-methylethyl)oxazolinyl]cyclopentadienyl, 1-C.3′-N}(η4-tetraphenylcyclobutadiene)cobalt]dipalladium (COP-X), containing bridging groups X = OAc, Cl, Br, I, O2/

Synthesis of pharmacologically relevant indoles with amine side chains via tandem hydroformylation/fischer indole synthesis

The sequence of hydroformylation and Fischer indole synthesis starting from amino olefins and aryl hydrazines is described. In a convergent manner, the two units bearing pharmacologically relevant substituents are assembled in the final indolization step. This modular and diversity-oriented approach to tryptamines and homotryptamines can be conducted in water and allows synthesis of branched and nonbranched tryptamines as well as tryptamine-based pharmaceuticals such as the 5-HT1D agonist L 775 606.