20306-86-9

Upstream product

• 108-05-4 vinyl acetate 
• 2941-20-0 1-phenylpropylamine 
• 52686-70-1 triethylamine-1-(2-naphthylethyl)borane 
• 75-05-8 acetonitrile 
• 2890-85-9 N-acetyl-1-phenylpropenamine 
• 60-35-5 acetamide 
• 93-55-0 1-phenyl-propan-1-one 
• 201230-82-2 carbon monoxide 
• 80-43-3 bis(1-methyl-1-phenylethyl)peroxide 
• 103-65-1 phenylpropane 
• 97305-96-9 (Z)-β-methyl-α-phenylacetyl enamide 
• 108-24-7 acetic anhydride 
• 125402-82-6 (E)-1-phenylpropanone O-benzyl oxime 
• 7484-41-5 4-(benzylideneamino)-3,4-dihydro-6-methyl-3-thioxo-1,2,4-triazin-5(2H)-one 

Downstream Products

• 19146-51-1 (S)-N-Acetylaminobutyric acid 
• 2941-20-0 1-phenylpropylamine 

Relevant academic research and scientific papers

Diazomethane Radical Cations as a Dipolarophile in the Dimeric Olefin Formation from Diazo-compounds

A novel cycloaddition mechanism involving diazomethane radical cations is proposed for the dimeric olefin formation by the one-electron oxidation of the diazo-compounds.The preference of cis-stilbene formation from phenyldiazomethane is understood by a secondary orbital interaction of phenyl groups on the cycloaddition step.

Reversal of chirality induced by m-methyl substitution of DIOP in the rhodium(I)-catalyzed asymmetric hydrogenation of α-phenyl-substituted enamides

Remarkable effects of the substituted diphenylphosphino groups of modified DIOPs on the enantioselectivity were observed in the asymmetric hydrogenation of α-phenyl-substituted enamides using their rhodium(I) complexes as catalysts. MOD-DIOP bearing p-met

Lipase/palladium-catalyzed asymmetric transformations of ketoximes to optically active amines.

[reaction: see text] Prochiral ketoximes were asymmetrically transformed to optically active amines in the acetylated forms by coupled lipase/palladium catalysis in the presence of an acyl donor under 1 atm of hydrogen.

Decarboxylative cross-nucleophile coupling via ligand-to-metal charge transfer photoexcitation of Cu(ii) carboxylates

Reactions that enable carbon–nitrogen, carbon–oxygen and carbon–carbon bond formation lie at the heart of synthetic chemistry. However, substrate prefunctionalization is often needed to effect such transformations without forcing reaction conditions. The development of direct coupling methods for abundant feedstock chemicals is therefore highly desirable for the rapid construction of complex molecular scaffolds. Here we report a copper-mediated, net-oxidative decarboxylative coupling of carboxylic acids with diverse nucleophiles under visible-light irradiation. Preliminary mechanistic studies suggest that the relevant chromophore in this reaction is a Cu(ii) carboxylate species assembled in situ. We propose that visible-light excitation to a ligand-to-metal charge transfer (LMCT) state results in a radical decarboxylation process that initiates the oxidative cross-coupling. The reaction is applicable to a wide variety of coupling partners, including complex drug molecules, suggesting that this strategy for cross-nucleophile coupling would facilitate rapid compound library synthesis for the discovery of new pharmaceutical agents. [Figure not available: see fulltext.].

Combined Theoretical and Experimental Studies Unravel Multiple Pathways to Convergent Asymmetric Hydrogenation of Enamides

We present a highly efficient convergent asymmetric hydrogenation of E/Z mixtures of enamides catalyzed by N,P-iridium complexes supported by mechanistic studies. It was found that reduction of the olefinic isomers (E and Z geometries) produces chiral amides with the same absolute configuration (enantioconvergent hydrogenation). This allowed the hydrogenation of a wide range of E/Z mixtures of trisubstituted enamides with excellent enantioselectivity (up to 99% ee). A detailed mechanistic study using deuterium labeling and kinetic experiments revealed two different pathways for the observed enantioconvergence. For α-aryl enamides, fast isomerization of the double bond takes place, and the overall process results in kinetic resolution of the two isomers. For α-alkyl enamides, no double bond isomerization is detected, and competition experiments suggested that substrate chelation is responsible for the enantioconvergent stereochemical outcome. DFT calculations were performed to predict the correct absolute configuration of the products and strengthen the proposed mechanism of the iridium-catalyzed isomerization pathway.

Biocatalytic, Intermolecular C?H Bond Functionalization for the Synthesis of Enantioenriched Amides

Directed evolution of heme proteins has opened access to new-to-nature enzymatic activity that can be harnessed to tackle synthetic challenges. Among these, reactions resulting from active site iron-nitrenoid intermediates present a powerful strategy to forge C?N bonds with high site- and stereoselectivity. Here we report a biocatalytic, intermolecular benzylic C?H amidation reaction operating at mild and scalable conditions. With hydroxamate esters as nitrene precursors, feedstock aromatic compounds can be converted to chiral amides with excellent enantioselectivity (up to >99 % ee) and high yields (up to 87 %). Kinetic and computational analysis of the enzymatic reaction reveals rate-determining nitrenoid formation followed by stepwise hydrogen atom transfer-mediated C?H functionalization.

Merging NiH Catalysis and Inner-Sphere Metal-Nitrenoid Transfer for Hydroamidation of Alkynes

The formal hydroamination/hydroamidation utilizing metal hydride is an appealing synthetic tool for the construction of valuable nitrogen-containing compounds from unsaturated hydrocarbons. While significant advances have been made for the functionalizations of alkenes in this realm, the direct hydroamidation of alkynes remains rather limited due to the high feasibility of the key metal-alkenyl intermediate to choose other reaction pathways. Herein, we report a NiH-catalyzed strategy for the hydroamidation of alkynes with dioxazolones, which allows convenient access to synthetically useful secondary enamides in (E)-anti-Markovnikov or Markovnikov selectivity. The reaction is viable for both terminal and internal alkynes and is also tolerant with a range of subtle functional groups. With H2O found as an essential component for high catalyst turnovers, the involvement of inner-sphere nitrenoid transfer is proposed that outcompetes an undesired semireduction process, thus representing the first example to show the competence of Ni catalysis for metal-nitrenoid formation from dioxazolones.

C-H Amination via Electrophotocatalytic Ritter-Type Reaction

A method for C-H bond amination via an electrophotocatalytic Ritter-Type reaction is described. The reaction is catalyzed by a trisaminocyclopropenium (TAC) ion in an electrochemical cell under irradiation. These conditions convert benzylic C-H bonds to acetamides without the use of a stoichiometric chemical oxidant. A range of functionality is shown to be compatible with this transformation, and several complex substrates are demonstrated.

Chemoselective formation of C–N bond in wet acetonitrile using amberlyst-15(H) as a recyclable catalyst

An economically efficient and environmentally benign protocol for the chemoselective one-pot synthesis of diversely N-substituted amides has been developed in good yield through the reaction of benzylic secondary alcohols as well as aliphatic tertiary alcohols and alkyl/aryl nitriles. Commercially available Amberlyst-15(H) has been utilized at 80 °C as an air-stable and reusable heterogeneous inexpensive solid acid catalyst without any anhydrous and inert environment. The attractive features of the present synthetic protocol are mild reaction conditions, short reaction time, excellent chemoselectivity, high atom economy and tolerance of various sensitive moieties.

Generation of amine dehydrogenases with increased catalytic performance and substrate scope from ε-deaminating L-Lysine dehydrogenase

Amine dehydrogenases (AmDHs) catalyse the conversion of ketones into enantiomerically pure amines at the sole expense of ammonia and hydride source. Guided by structural information from computational models, we create AmDHs that can convert pharmaceutically relevant aromatic ketones with conversions up to quantitative and perfect chemical and optical purities. These AmDHs are created from an unconventional enzyme scaffold that apparently does not operate any asymmetric transformation in its natural reaction. Additionally, the best variant (LE-AmDH-v1) displays a unique substrate-dependent switch of enantioselectivity, affording S- or R-configured amine products with up to >99.9% enantiomeric excess. These findings are explained by in silico studies. LE-AmDH-v1 is highly thermostable (Tm of 69 °C), retains almost entirely its catalytic activity upon incubation up to 50 °C for several days, and operates preferentially at 50 °C and pH 9.0. This study also demonstrates that product inhibition can be a critical factor in AmDH-catalysed reductive amination.