776-99-8Relevant academic research and scientific papers
Transaminase-mediated synthesis of enantiopure drug-like 1-(3′,4′-disubstituted phenyl)propan-2-amines
Lakó, ágnes,Mendon?a, Ricardo,Molnár, Zsófia,Poppe, László
, p. 40894 - 40903 (2020/11/23)
Transaminases (TAs) offer an environmentally and economically attractive method for the direct synthesis of pharmaceutically relevant disubstituted 1-phenylpropan-2-amine derivatives starting from prochiral ketones. In this work, we report the application of immobilised whole-cell biocatalysts with (R)-transaminase activity for the synthesis of novel disubstituted 1-phenylpropan-2-amines. After optimisation of the asymmetric synthesis, the (R)-enantiomers could be produced with 88-89% conversion and >99% ee, while the (S)-enantiomers could be selectively obtained as the unreacted fraction of the corresponding racemic amines in kinetic resolution with >48% conversion and >95% ee. This journal is
Cleavage of CC and Co bonds in β-O-4 linkage of lignin model compound by cyclopentadienone group 8 and 9 metal complexes
Kishino, Masamichi,Kusumoto, Shuhei,Nozaki, Kyoko
supporting information, p. 477 - 480 (2020/05/19)
Degradation of 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphe-noxy)propane-1,3-diol (1), a model compound for lignin β-O-4 linkage was examined with iron, ruthenium, rhodium and iridium complexes bearing cyclopentadienone ligand. Cyclopentadienone iron complex gave only a small amount of degraded product with reduced molecular weight. Cyclopentadienone ruthenium complex, so called Shvo's catalyst, afforded 3,4-dimethoxybenzaldehyde (a3) in 14.3% yield after CαCβ bond cleavage. On the other hand, cyclopentadienone group-9 metal complexes catalyzed CβO bond cleavage to afford guaiacol (b1) as a main product in up to 74.9% yield.
α-C-H borylation of secondary alcohols: Via Ru/Fe relay catalysis: Building a platform for alcoholic C-H/C-O functionalizations
Zhu, Qing,He, Zeyu,Wang, Lu,Hu, Yue,Xia, Chungu,Liu, Chao
supporting information, p. 11884 - 11887 (2019/10/11)
An unprecedented α-C-H borylation of secondary alcohols was successfully achieved and delivered various tertiary α-boryl alcohols via [Ru]/[Fe] relay catalysis. The dehydrogenation catalyst (Ru) and borylation catalyst (Fe) interacted to increase the chemoselectivity. By installing the "platform functional group" Bpin via this α-C-H borylation, several alcoholic α-C-H and C-O bond functionalizations were successfully achieved.
Stereoselective Synthesis of 1-Arylpropan-2-amines from Allylbenzenes through a Wacker-Tsuji Oxidation-Biotransamination Sequential Process
González-Martínez, Daniel,Gotor, Vicente,Gotor-Fernández, Vicente
, p. 2582 - 2593 (2019/05/15)
Herein, a sequential and selective chemoenzymatic approach is described involving the metal-catalysed Wacker-Tsuji oxidation of allylbenzenes followed by the amine transaminase-catalysed biotransamination of the resulting 1-arylpropan-2-ones. Thus, a series of nine optically active 1-arylpropan-2-amines were obtained with good to very high conversions (74–92%) and excellent selectivities (>99% enantiomeric excess) in aqueous medium. The Wacker-Tsuji reaction has been exhaustively optimised searching for compatible conditions with the biotransamination experiments, using palladium(II) complexes as catalysts and iron(III) salts as terminal oxidants in aqueous media. The compatibility of palladium/iron systems for the chemical oxidation with commercially available and made in house amine transaminases was analysed, finding ideal conditions for the development of a general and stereoselective cascade sequence. Depending on the selectivity displayed by selected amine transaminase, it was possible to produce both 1-arylpropan-2-amines enantiomers under mild reaction conditions, compounds that present therapeutic properties or can be employed as synthetic intermediates of chiral drugs from the amphetamine family. (Figure presented.).
1-aryl-2-acetone compound preparation method
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Paragraph 0041-0042, (2020/01/08)
The invention discloses a 1-aryl-2-acetone compound preparation method, which comprises: (1) carrying out a reaction on (E)-2-methyl-3-aryl acrylic acid (I) as a starting raw material and diphenyl azidophosphate (DPPPA) in the presence of an organic alkali; (2) carrying out a heating reaction; and (3) adding an acidic aqueous solution into the reaction solution, and carrying out a reaction to obtain the 1-aryl-2-acetone compound with a structural formula (IV). According to the present invention, the method can solve the technical problems of difficultly available, highly-corrosive, highly toxic and highly explosive reagents, long steps, low yield, tedious operation and the like in the 1-aryl-2-acetone synthesis in the prior art, has characteristics of easily available raw materials, safe and simple operation, mild condition and high yield, and is suitable for industrial production.
A convenient and efficient one-pot synthesis of arylacetones from (E)-3-aryl-2-methylacrylic acids by curtius rearrangement
He, Xin,Cao, Chong,Liang, Jingwei,Li, Xinyang,Zhang, Tingjian,Meng, Fanhao
, p. 386 - 390 (2017/02/10)
A convenient and efficient method was developed for the synthesis of arylacetones from (E)-3-aryl-2-methylacrylic acids through a Curtius rearrangement. The Curtius rearrangement of (E)-3-aryl-2-methylacryloyl azides and subsequent hydrolysis proceeded at mild temperatures in a two-phase medium of carbon tetrachloride and water containing a catalytic amount of tetrabutylammonium bromide to give the corresponding derivatives in 82-93% yield.
A method of preparing veratryl acetone (by machine translation)
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Paragraph 0027; 0028, (2016/10/17)
The invention discloses a method for preparing of acetone veratryl, is the by-product of the to the benzofuranol 4 - (2-methyl propyl) - 1,2-dihydroxybenzene and methane chloride as the raw material, with a strong base as acid-binding agent, in a solvent of water, and phase transfer catalyst under a high pressure condition by etherification reaction intermediates of the 1,2-dimethoxy-4 - (2-methyl-propyl) benzene. Then 1,2-dimethoxy-4 - (2-methyl-propyl) benzene in the solvent acetic acid in the oxidation reaction with ozone, then the reduction with zinc powder, products prepared veratryl acetone. Reaction formula is as follows: The invention has realized the utilization of waste material, to meet the environmental protection, the requirements of economic development cycle. The resulting intermediate 4 - (2-methyl propyl) - 1,2-dihydroxybenzene quality is high, the preparation of high-quality products to lay a good foundation for veratryl acetone. The process is simple, the operation is convenient, easy availability of raw materials, the production cost is cheap, is beneficial for the industrial production. The product yield is high, the total yield is greater than 70%, the product quality is high, quality content 98% or more. (by machine translation)
Preparation method for aryl acetone compounds
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Paragraph 0038; 0039, (2017/03/08)
The invention belongs to the field of organic synthesis, and specifically relates to a preparation method for aryl acetone compounds. A technical scheme of the invention is as follows: (1) with 2-methyl-3-arylacrylic acid as a starting material, carrying out a catalytic reaction of the starting material and thionyl chloride in an organic solvent through a catalyst so as to obtain 2-methyl-3-aryl acryloyl chloride, carrying out reduced pressure distillation so as to remove the organic solvent, then adding methanol, and carrying out a reaction so as to obtain methyl 2-methyl-3-arylacrylate; (2) adding hydrazine hydrate with a concentration of 80% into a reaction solution in the step 1, and carrying out a reaction so as to obtain a 2-methyl-3-aryl acrylyl hydrazine; and (3) subjecting a reaction solution in the step 2 to reduced pressure distillation so as to remove methanol, then adding the organic solvent and diluted hydrochloric acid and carrying out stirring, taking sodium nitrite and carrying out preparing into an aqueous solution, and dropwise adding the aqueous solution of sodium nitrite into a system under stirring so as to prepare aryl acetone. The method provided by the invention has the advantages of low production cost, mild reaction conditions, simple operation, high yield, and applicability to industrial production.
Greening the Wacker process
Kulkarni, Mukund G.,Shaikh, Yunnus B.,Borhade, Ajit S.,Chavhan, Sanjay W.,Dhondge, Attrimuni P.,Gaikwad, Dnyaneshwar D.,Desai, Mayur P.,Birhade, Deekshaputra R.,Dhatrak, Nagorao R.
supporting information, p. 2293 - 2295 (2013/06/26)
Wacker oxidation of various terminal olefins with Pd0/C- KBrO3, a nontoxic, environmentally benign, and easy to handle catalyst system, was achieved in high isolated yields. The described protocol offers an alternative to the traditional Wacker system which uses CuCl 2 as co-catalyst. The catalyst is reusable while maintaining high activity and selectivity.
Palladium-catalyzed mono-α-arylation of acetone with aryl halides and tosylates
Hesp, Kevin D.,Lundgren, Rylan J.,Stradiotto, Mark
supporting information; experimental part, p. 5194 - 5197 (2011/06/10)
We report the first example of selective Pd-catalyzed mono-α- arylation of acetone employing aryl chlorides, bromides, iodides, and tosylates. The use of appropriately designed P,N-ligands proved to be the key to controlling the reactivity and selectivity. The reaction affords good yields with substrates containing a range of functional groups at modest Pd loadings using Cs2CO3 as the base and employing acetone as both a reagent and the solvent.(Figure Presented)
