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Upstream product

• 117266-34-9 (E)-N-((E)-4-phenylbut-3-en-2-ylidene)aniline 
• 316122-26-6 N-((E)-4-phenylbut-3-en-2-ylidene)aniline 
• 62-53-3 aniline 
• 98-80-6 phenylboronic acid 
• 32644-22-7 1-methyl-3-phenylallene 
• 81176-43-4 (S)-trans-4-phenyl-3-buten-2-ol 
• 93588-88-6 1-pentyl-3-pentylallene 
• 588-73-8 (Z)-β-bromostyrene 
• 16939-57-4 (E)-buta-1,3-dienylbenzene 
• 36004-04-3 ethyl (E)-1-phenylbut-1-en-3-ol 
• 51616-91-2 (-)-(S,E)-4-Phenylbut-3-en-2-ylamin 

Relevant academic research and scientific papers

Tsuji–Trost Reaction of Non-Derivatized Allylic Alcohols

Palladium-catalyzed allylic substitution of non-derivatized enantioenriched allylic alcohols with a variety of uncharged N-, S-, C- and O-centered nucleophiles using a bidentate BiPhePhos ligand is described. A remarkable effect of the counter ion (X) of the XPd[κ2-BiPhePhos][η3-C3H5] was observed. When ClPd[κ2-BiPhePhos][η3-C3H5] (complex I) was used as catalyst, non-reproducible results were obtained. Study of the complex by X-ray crystallography, 31P NMR spectroscopy, and ESI-MS showed that a decomposition occurred where one of the phosphite ligands was oxidized to the corresponding phosphate, generating ClPd[κ1-BiPhePhosphite-phosphate][η3-C3H5] species (complex II). When the chloride was exchanged to the weaker coordinating OTf? counter ion the more stable Pd[κ2-BiPhePhos][η3-C3H5]++[OTf] ? (complex III) was formed. Complex III performed better and gave higher enantiospecificities in the substitution reactions. Complex III was evaluated in Tsuji–Trost reactions of stereogenic non-derivatized allylic alcohols. The desired products were obtained in good to excellent yields (71–98 %) and enantiospecificities (73–99 %) for both inter- and intramolecular substitution reactions with only water generated as a by-product. The methodology was applied to key steps in total synthesis of (S)-cuspareine and (+)-lentiginosine. A reaction mechanism involving a palladium hydride as a key intermediate in the activation of the hydroxyl group is proposed in the overall transformation.

Enantioselective Intermolecular Addition of Aliphatic Amines to Acyclic Dienes with a Pd-PHOX Catalyst

We report a method for the catalytic, enantioselective intermolecular addition of aliphatic amines to acyclic 1,3-dienes. In most cases, reactions proceed efficiently at or below room temperature in the presence of 5 mol % of a Pd catalyst bearing a PHOX ligand, generating allylic amines in up to 97:3 er. The presence of an electron-deficient phosphine within the ligand not only leads to a more active catalyst but also is critical for achieving high site selectivity in the transformation.

Enantioselective, Stereodivergent Hydroazidation and Hydroamination of Allenes Catalyzed by Acyclic Diaminocarbene (ADC) Gold(I) Complexes

The gold-catalyzed enantioselective hydroazidation and hydroamination reactions of allenes are presented herein. ADC gold(I) catalysts derived from BINAM were critical for achieving high levels of enantioselectivity in both transformations. The sense of enantioinduction is reversed for the two different nucleophiles, allowing access to both enantiomers of the corresponding allylic amines using the same catalyst enantiomer. Chiral allylic azides and amines are obtained by enantioselective hydroazidation and hydroamination of allenes catalyzed by acyclic diaminocarbene gold(I) catalysts derived from BINAM. The sense of enantioinduction is reversed for the two different nucleophiles, allowing easy access to both enantiomers with a single catalyst enantiomer.

Deammoniative condensation of primary allylic amines with nonallylic amines

An unprecedented deammoniative condensation reaction of primary allylic amines with nonallylic amines has been developed through C-N bond cleavage. In the presence of 5 mol% palladium diacetate, 10 mol% 1,4-bis(diphenylphosphino) butane (dppb), and 5 mol% p-toluenesulfonic acid (TsOH), a range of α-unbranched primary allylic amines smoothly underwent deammoniative condensation with nonallylic amines in an α-selective fashion to give structurally diverse secondary and tertiary amines in good to excellent yields and E selectivity. Replacing dppb with racemic 2,2-bis(diphenylphosphino)-1,1- binaphthyl (BINAP) permitted the deammoniative condensation of enantioenriched α-chiral primary allylic amines with nonallylic amines to proceed with complete retention of configuration. Electrospray ionization (ESI) mass spectrometric analysis of the reaction mixture permitted the identification of some π-allylpalladium intermediates, and plausible mechanisms have been proposed to account for the regioselectivity and stereospecificity of the deammoniative condensation reaction. A range of enantioenriched primary allylic amines underwent palladium/acid-catalyzed direct substitution with nonallylic amines in a stereospecific manner. Copyright

Cooperative catalysis by palladium and a chiral phosphoric acid: Enantioselective amination of racemic allylic alcohols

Cooperative catalysis by [Pd(dba)2] and the chiral phosphoric acid BA1 in combination with the phosphoramidite ligand L8 enabled the efficient enantioselective amination of racemic allylic alcohols with a variety of functionalized amines. This

Formamides derived from N-methyl amino acids serve as new chiral organocatalysts in the enantioselective reduction of aromatic ketimines with trichlorosilane

Asymmetric reduction of N-aryl ketimines 1a-k, 43, and 45 with trichlorosilane can be catalyzed by new N-methyl l-amino acid-derived Lewis-basic organocatalysts, such as the valine-derived bisamide 3d (10 mol%), in toluene at room temperature with high enantioselectivity (≤92% ee). The structure-reactivity investigation shows that the product configuration is controlled by the nature of the side chain of the catalyst scaffold (e.g., i-Pr vs Me, as in 3d and 6e), so that catalysts of the same absolute configuration may induce the formation of the opposite enantiomers of the product. Arene-arene interactions between the catalyst and the incoming imine appear to be the prerequisite for asymmetric induction. This metal-free, organocatalytic protocol is competitive with the traditional, metal-catalyzed methodology.

Gold-catalyzed intermolecular hydroamination of allenes with arylamines and resulting high chirality transfer

(Chemical Equation Presented) Au contraire! Contrary to the relatively well-studied metal-catalyzed intramolecular hydroamination of allenes, the intermolecular reaction is rare and is here accomplished with a gold (III) catalyst. Aryl amines 2 react with

Regioselective iron-catalyzed allylic amination

(Chemical Equation Presented) Iron age: An air- and water-resistant iron(-II) catalyst, in the presence of triphenylphosphane under buffered conditions, allows for the highly regioselective and stereoselective allylation of primary aromatic amines. A broa

A highly enantioselective Lewis basic organocatalyst for reduction of N-aryl imines with unprecedented substrate spectrum

L-Pipecolinic acid derived formamides have been developed as highly efficient and enantioselective Lewis basic organocatalysts for the reduction of N-aryl imines with trichlorosilane. Catalyst 4b afforded high isolated yields (up to 98%) and enantioselect