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Ethoxycarbonyl cyanohydrins and -acyl cyanohydrins are examples of -protected cyanohydrins in which the protecting group presents an electrophilic center, contributing to additional reaction pathways. The first section of this review describes recent advances on the synthesis of -ethoxycarbonyl and -acyl protected cyanohydrins. Reactions using KCN or alkyl cyanoformates as the cyanide ion source are described, as well as organic and transition metal catalysis used in their preparation, including asymmetric cyanation. In a second part, transformations, and synthetic applications of -ethoxycarbonyl/acyl cyanohydrins are presented. A variety of structures has been obtained starting from such protected cyanohydrins and, in particular, the synthesis of oxazoles, 1,4-diketones, 1,3-diketones, 2-vinyl-2-cyclopentenones through various methods are discussed.
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http://dx.doi.org/10.3390/molecules26154691 | DOI Listing |
A diastereoselective organocatalytic synthesis of ()- and ()-methoxycarbonylhydroxymethyluridines (mchmUs) and their acid analogues (chmUs) was developed. The method employs organo- and organometallic-catalyzed cyanosilylation of 5-formyluridine to yield diastereomerically enriched TMS-protected cyanohydrins, which are converted a Pinner reaction to ()- and ()-mchmUs, then hydrolyzed to ()- and ()-chmUs.
View Article and Find Full Text PDFChemistry
February 2025
Department of Chemistry, Nano-Science Center, University of Copenhagen, Universitetsparken 5, Copenhagen Ø, 2100, Denmark.
The atmospheric concentration of carbon dioxide (CO) has fluctuated throughout Earth's history. However, the role of CO in prebiotic chemistry has been predominantly and limitedly postulated as a C1 precursor, which can be reduced to carbon monoxide or methane mimicking the Wood-Ljungdahl pathway. Herein we present neglected roles of CO as an active promoter in accessing biologically important C3-builidng blocks such as lactate, via redox-economic reaction cycles starting from cyanide (C1) and acetaldehyde (C2).
View Article and Find Full Text PDFBioorg Med Chem Lett
September 2024
Department of Chemistry, UFPR, Paraná, Brazil. Electronic address:
A series of seleno-containing polyfunctionalized compounds was synthesized exploring cyanohydrin chemistry, including α-hydroxy esters, α-hydroxy acids, 1,2-diols, and 1,2-diacetates, with yields ranging from 26 up to 99 %. The cytotoxicity of all synthesized compounds was then evaluated using a non-tumor cell line (BALB/3T3 murine fibroblasts), and those deemed non-cytotoxic had their anti-melanoma activity evaluated using B16-F10 murine melanoma cells. These assays identified two compounds with selective cytotoxic activity against the tested melanoma cell line, showing a potential anti-melanoma application.
View Article and Find Full Text PDFACS Cent Sci
February 2023
Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
Automation and digitalization solutions in the field of small molecule synthesis face new challenges for chemical reaction analysis, especially in the field of high-performance liquid chromatography (HPLC). Chromatographic data remains locked in vendors' hardware and software components, limiting their potential in automated workflows and data science applications. In this work, we present an open-source Python project called MOCCA for the analysis of HPLC-DAD (photodiode array detector) raw data.
View Article and Find Full Text PDFCommun Chem
March 2022
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-Katsura, Nishikyo, Kyoto, 615-8510, Japan.
The asymmetric cyanation of acylsilanes affords densely functionalized tetrasubstituted chiral carbon centers bearing silyl, cyano, and hydroxy groups, which are of particular interest in synthetic and medicinal chemistry. However, this method has been limited to a few enzymatic approaches, which employ only one substrate because of substrate specificity. Here we show the non-enzymatic catalytic asymmetric cyanation of acylsilanes using a chiral Lewis base as an enantioselective catalyst, trimethylsilyl cyanide as a cyanating reagent, and isopropyl alcohol as an additive to drive catalyst turnover.
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