13275-31-5Relevant articles and documents
REACTION OF ORGANOCADMIUM REAGENTS WITH ETHYL CYANOFORMATE: PREPARATION OF α-KETO ESTERS
Akiyama, Yasunobu,Kawasaki, Tomomi,Sakamoto, Masanori
, p. 1231 - 1232 (1983)
Organocadmium reagents reacted with the cyano-function of ethyl cyanoformate in the presence of ZnCl2 to afford the corresponding α-keto esters.
A convenient preparation of α-keto esters by the Grignard reaction on N-acylpyrazoles
Kashima, Choji,Shirahata, Yoshie,Tsukamoto, Yoshihiro
, p. 459 - 464 (1998)
The α-keto esters were prepared by the formation of N-acylpyrazole followed by the appropriate Grignard reaction. These short step reaction conveniently afforded various α-keto esters in good yields.
Biocatalytic Construction of Quaternary Centers by Aldol Addition of 3,3-Disubstituted 2-Oxoacid Derivatives to Aldehydes
Marín-Valls, Roser,Hernández, Karel,Bolte, Michael,Parella, Teodor,Joglar, Jesús,Bujons, Jordi,Clapés, Pere
supporting information, p. 19754 - 19762 (2020/12/01)
The congested nature of quaternary carbons hinders their preparation, most notably when stereocontrol is required. Here we report a biocatalytic method for the creation of quaternary carbon centers with broad substrate scope, leading to different compound classes bearing this structural feature. The key step comprises the aldol addition of 3,3-disubstituted 2-oxoacids to aldehydes catalyzed by metal dependent 3-methyl-2-oxobutanoate hydroxymethyltransferase from E. coli (KPHMT) and variants thereof. The 3,3,3-trisubstituted 2-oxoacids thus produced were converted into 2-oxolactones and 3-hydroxy acids and directly to ulosonic acid derivatives, all bearing gem-dialkyl, gem-cycloalkyl, and spirocyclic quaternary centers. In addition, some of these reactions use a single enantiomer from racemic nucleophiles to afford stereopure quaternary carbons. The notable substrate tolerance and stereocontrol of these enzymes are indicative of their potential for the synthesis of structurally intricate molecules.
Domino Synthesis of α,β-Unsaturated γ-Lactams by Stereoselective Amination of α-Tertiary Allylic Alcohols
Xie, Jianing,Xue, Sijing,Escudero-Adán, Eduardo C.,Kleij, Arjan W.
, p. 16727 - 16731 (2018/11/23)
Tertiary allylic alcohols equipped with a carboxyl group can be smoothly aminated under ambient conditions by a conceptually new and stereoselective protocol under palladium catalysis. The in situ formed Z-configured γ-amino acid cyclizes to afford an α,β-unsaturated γ-lactam, releasing water as the only byproduct. This practical catalytic transformation highlights the use of a carboxyl group acting as an activating and stereodirecting functional group to provide a wide series of pharma-relevant building blocks. Various control reactions support the crucial role of the carboxyl group in the substrate to mediate these transformations.
Switchable C-H Functionalization of N-Tosyl Acrylamides with Acryloylsilanes
Song, Shengjin,Lu, Ping,Liu, Huan,Cai, Sai-Hu,Feng, Chao,Loh, Teck-Peng
supporting information, p. 2869 - 2872 (2017/06/13)
A controllable Rh-catalyzed protocol to access alkylation and alkenylation-annulation of N-tosyl acrylamide with acryloyl silane is reported. In contrast to the directing group or catalyst-dependent divergent sp2 C-H alkylation/alkenylation, the intrinsic property of acryloylsilane allows the switchable reaction manifold, thereby affording either alkylation or annulation products with slight modification of the reaction conditions.
As opioid receptor antagonists or inverse agonists of the novel compounds
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Paragraph 0272-0274, (2016/10/08)
Novel compounds which are antagonists or inverse agonists at one or more of the opioid receptors, pharmaceutical compositions containing them, to processes for their preparation.
SYNTHESIS METHOD FOR L-CYCLIC ALKYL AMINO ACID AND PHARMACEUTICAL COMPOSITION HAVING THEREOF
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Paragraph 0070-0071, (2016/11/17)
A synthesis method for L-cyclic alkyl amino acid and a pharmaceutical composition having the said amino acid are provide in the present disclosure provides. The synthesis method comprises: step A.) preparing a cyclic alkyl keto acid or a cyclic alkyl keto acid salt having Structural Formula (I) or Structural Formula (II), and step B.) mixing the cyclic alkyl keto acid or the cyclic alkyl keto acid salt with ammonium formate, a leucine dehydrogenase, a formate dehydrogenase and a coenzyme NAD+, and carrying out a reductive amination reaction to generate the L-cyclic alkyl amino acid, wherein the Structural Formula (I) is where n1≧1, m1≧0 and the M1 is H or a monovalent cation; the Structural Formula (II) is where n2≧0, m2≧0, the M2 is H or a monovalent cation, an amino acid sequence of the leucine dehydrogenase is SEQ ID No.1.
Catalytic formal cycloadditions between anhydrides and ketones: Excellent enantio and diastereocontrol, controllable decarboxylation and the formation of adjacent quaternary stereocentres
Cornaggia, Claudio,Gundala, Sivaji,Manoni, Francesco,Gopalasetty, Nagaraju,Connon, Stephen J.
supporting information, p. 3040 - 3046 (2016/03/19)
It has been shown for the first time that enolisable anhydrides can participate in highly efficient and diastereo/enantioselective additions to activated ketones. In these reactions the anhydride component formally acts (initially) as the nucleophilic component. These processes are promoted by novel, readily prepared urea-substituted cinchona alkaloid-derived catalysts at low loadings under mild conditions. Three classes of enolisable anhydride and three different types of activated ketone were shown to be compatible with the process-generating a diverse range of structurally distinct and densely functionalised lactone products with the formation of two new stereocentres, one of which is quaternary. In one example, a product incorporating two contiguous quaternary stereocentres (one all carbon) was formed with outstanding enantiocontrol. It has been shown in the case of glutaconic anhydride derivatives that the cycloaddtion process is reversible, and can be accompanied by decarboxylation and olefin isomerisation. Reaction conditions can be modified to give access to three types of product with good-excellent ee.
Rhodium(iii)-catalyzed C-H allylation of electron-deficient alkenes with allyl acetates
Feng, Chao,Feng, Daming,Loh, Teck-Peng
supporting information, p. 342 - 345 (2015/01/09)
Rhodium-catalyzed C-H allylation of acrylamides with allyl acetates is reported. The use of weakly coordinating directing group resulted in high reaction efficiency, broad functionality tolerance and excellent γ-selectivity, which opens a new synthetic pathway for the access of 1,4-diene skeletons.
SOLUBLE GUANYLATE CYCLASE ACTIVATORS
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Page/Page column 38; 39, (2015/06/25)
A compound of Formula I or a pharmaceutically acceptable salt thereof, are capable of modulating the body's production of cyclic guanosine monophosphate (" cGMP") and are generally suitable for the therapy and prophylaxis of diseases which are associated with a disturbed cGMP balance. The invention furthermore relates to processes for preparing compounds of Formula I, or a pharmaceuticall acceptable salt thereof, for their use in the therapy and prophylaxis of the abovementioned diseases and for preparing pharmaceuticals for this purpose, and to pharmaceutical preparations which comprise compounds of Formula I or a pharmaceutically acceptable salt thereof.
