2985-39-9Relevant articles and documents
Decarboxylative Mannich Reactions with Substituted Malonic Acid Half-Oxyesters
Xavier, Tania,Condon, Sylvie,Pichon, Christophe,Le Gall, Erwan,Presset, Marc
, p. 5452 - 5462 (2021/05/07)
The decarboxylative Mannich reaction between imines and substituted malonic acids half-oxyesters (SMAHOs) has been developed using 1,4-diazabicyclo[2.2.2]octane (DABCO) as an organocatalyst. The reaction proceeds under simple reaction conditions and toler
Preparation of mono-substituted malonic acid half oxyesters (SMAHOs)
Condon, Sylvie,Le Gall, Erwan,Pichon, Christophe,Presset, Marc,Xavier, Tania
supporting information, p. 2085 - 2094 (2021/09/02)
The use of mono-substituted malonic acid half oxyesters (SMAHOs) has been hampered by the sporadic references describing their preparation. An evaluation of different approaches has been achieved, allowing to define the best strategies to introduce diversity on both the malonic position and the ester function. A classical alkylation step of a malonate by an alkyl halide followed by a monosaponification gave access to reagents bearing different substituents at the malonic position, including functionalized derivatives. On the other hand, the development of a monoesterification step of a substituted malonic acid derivative proved to be the best entry for diversity at the ester function, rather than the use of an intermediate Meldrum acid. Both these transformations are characterized by their simplicity and efficiency, allowing a straightforward access to SMAHOs from cheap starting materials.
Hydrogen-Bonding Assisted Catalytic Kinetic Resolution of Acyclic β-Hydroxy Amides
Porey, Arka,Mondal, Bhaskar Deb,Guin, Joyram
supporting information, p. 8786 - 8791 (2021/03/17)
Enantioenriched acyclic α-substituted β-hydroxy amides are valuable compounds in chemical, material and medicinal sciences, but their enantioselective synthesis remains challenging. A catalytic kinetic resolution (KR) of such amides with selectivity factor(s) up to >200 is developed via enantioselective acylation of primary alcohol with N-heterocyclic carbene. An enhanced selectivity for the catalytic KR process is realized using cyclic tertiary amine as base additive. Diastereomeric transition state models for the process are proposed to rationalize the origin of enantioselectivity.
Cobalt-Catalyzed Highly Regioselective Three-Component Arylcarboxylation of Acrylate with Aryl Bromides and Carbon Dioxide
Hang, Wei,Liang, Nianjie,Liu, Yuzhou,Xi, Chanjuan
, p. 4941 - 4946 (2021/10/30)
Cobalt-catalyzed regioselective three-component arylcarboxylation of acrylate with aryl bromides and carbon dioxide has been developed. The reaction is carried out by using cobalt chloride as a precatalyst and zinc powder as a reducing reagent under CO2 (1 atm) at 40 °C. A range of aryl bromides are used for this reaction, leading to a series of valuable carboxylic acids with high regioselectivity and functional-group compatibility. Mechanistic experiments and DFT calculations indicate that this arylcarboxylation reaction involves the reaction of CO2 with a cobalt enolate intermediate to form the C?C bond.
Enantioselective α-Amination of Acyclic 1,3-Dicarbonyls Catalyzed by N-Heterocyclic Carbene
Santra, Surojit,Maji, Ujjwal,Guin, Joyram
supporting information, p. 468 - 473 (2020/02/04)
Herein, we describe a method for the catalytic enantioselective α-amination of α-substituted acyclic 1,3-ketoamides and 1,3-amidoesters that affords the products possessing N-substituted quaternary stereocenters with a chiral N-heterocyclic carbene (NHC). The reaction is based on the utilization of an intrinsic Br?nsted base characteristic of NHC that enables the catalytic formation of a chiral ion pair comprising the enolate and the azolium ion. A series of challenging open-chain α-substituted 1,3-dicarbonyls are aminated via this method with ee's of ≤99%.
Double decarboxylative route to 3-substituted pyrrolidines: Reaction of monoalkyl malonates and related carboxylic acids with sarcosine and formaldehyde
Buev, Evgeny M.,Smorodina, Anastasia A.,Moshkin, Vladimir S.,Sosnovskikh, Vyacheslav Y.
supporting information, (2020/02/22)
Three-component reactions of monoalkyl malonates, cyanoacetic acids or 2-ketocarboxylic acids, N-methylglycine, and formaldehyde were developed to rapidly access 3-substituted pyrrolidines in 17–97% yield. These reactions represent a double decarboxylative domino-sequence promoted by pyrrolidine and involve N-methylazomethine ylide as the reactive intermediate.
Synthesis of protected α-amino acids: Via decarboxylation amination from malonate derivatives
Dai, Qipu,Fu, Hui,Hu, Changwen,Li, Peihe,Li, Xiaoying,Wang, Zheng
, p. 4439 - 4446 (2020/10/20)
A general and efficient strategy for the synthesis of protected α-amino acids is reported. The method uses malonate derivatives as the starting materials and Cs2CO3 as a base at 60 degrees, giving α-amino acid derivatives in moderate yields by releasing CO2. This methodology shows broad substrate scope (primary and secondary acids), excellent functional group tolerance and high efficiency to give the desired products under mild reaction conditions. It also allows the construction of β and γ-amino acids and other unnatural products.
Synthesis of α,β-Disubstituted Acrylates via Galat Reaction
Xavier, Tania,Condon, Sylvie,Pichon, Christophe,Le Gall, Erwan,Presset, Marc
supporting information, p. 6135 - 6139 (2019/08/28)
Galat reactions between aldehydes and substituted malonic acids half oxyester were found to be efficiently catalyzed by morpholine in refluxing toluene. This transformation allows the stereoselective synthesis of diverse α,β-disubstituted acrylates in moderate to good yields. This method constitutes an attractive alternative to existing methods in terms of scope and eco-compatibility.
Photo-induced Decarboxylative Heck-Type Coupling of Unactivated Aliphatic Acids and Terminal Alkenes in the Absence of Sacrificial Hydrogen Acceptors
Cao, Hui,Jiang, Heming,Feng, Hongyu,Kwan, Jeric Mun Chung,Liu, Xiaogang,Wu, Jie
supporting information, p. 16360 - 16367 (2018/11/27)
1,2-Disubstituted alkenes such as vinyl arenes, vinyl silanes, and vinyl boronates are among the most versatile building blocks that can be found in every sector of chemical science. We herein report a noble-metal-free method of accessing such olefins through a photo-induced decarboxylative Heck-type coupling using alkyl carboxylic acids, one of the most ubiquitous building blocks, as the feedstocks. This transformation was achieved in the absence of external oxidants through the synergistic combination of an organo photo-redox catalyst and a cobaloxime catalyst, with H2 and CO2 as the only byproducts. Both control experiments and DFT calculations supported a radical-based mechanism, which eventually led to the development of a selective three-component coupling of aliphatic carboxylic acids, acrylates, and vinyl arenes. More than 90 olefins across a wide range of functionalities were effectively synthesized with this simple protocol.
Molecular tools that block maturation of the nuclear lamin A and decelerate cancer cell migration
Matralis, Alexios N.,Xanthopoulos, Dimitrios,Huot, Geneviève,Lopes-Paciencia, Stéphane,Cole, Charles,de Vries, Hugo,Ferbeyre, Gerardo,Tsantrizos, Youla S.
supporting information, p. 5547 - 5554 (2018/10/15)
Lamin A contributes to the structure of nuclei in all mammalian cells and plays an important role in cell division and migration. Mature lamin A is derived from a farnesylated precursor protein, known as prelamin A, which undergoes post-translational cleavage catalyzed by the zinc metalloprotease STE24 (ZPMSTE24). Accumulation of farnesylated prelamin A in the nuclear envelope compromises cell division, impairs mitosis and induces an increased expression of inflammatory gene products. ZMPSTE24 has been proposed as a potential therapeutic target in oncology. A library of peptidomimetic compounds were synthesized and screened for their ability to induce accumulation of prelamin A in cancer cells and block cell migration in pancreatic ductal adenocarcinoma cells. The results of this study suggest that inhibitors of lamin A maturation may interfere with cell migration, the biological process required for cancer metastasis.
