Xylochemical Synthesis of Cytotoxic 2-Aminophenoxazinone-Type Natural Products Through Oxidative Cross Coupling

Today, the total synthesis of natural products mostly relies on the use of petroleum-based starting materials. The commercial availability of building blocks of this type often deflects attention away from lengthy synthetic routes required for the reintroduction of heteroatom substitution patterns lost in the geological process of kerogenesis. Herein, the use of wood-based starting materials, the so-called xylochemicals, for the synthesis of 2-aminophenoxazinone natural products is presented. The inherent heteroatom substitution patterns as well as chemical functionalities were employed and permitted a short and straightforward synthetic strategy. Moreover, a novel and “green” method for co…

Making natural products from renewable feedstocks: back to the roots?

Covering: up to mid-2019 This review highlights the utilization of biomass-derived building blocks in the total synthesis of natural products. An overview over several renewable feedstock classes, namely wood/lignin, cellulose, chitin and chitosan, fats and oils, as well as terpenes, is given, covering the time span from the initial beginning of natural product synthesis until today. The focus is put on the origin of the employed carbon atoms and on the nature of the complex structures that were assembled therefrom. The emerging trend of turning away from petrochemically derived starting materials back to bio-based resources, just as seen in the early days of total synthesis, shall be demon…

A New Flavonol Glycoside from Tristemma hirtum (Melastomataceae)

A Photoredox-Catalyzed Four Component Reaction for the Atom-Efficient Synthesis of Complex Secondary Amines

The one-pot sulfonylation/aminoalkylation of styrene derivatives furnishing highly substituted gamma-sulfonylamines was accomplished through a photoredox-catalyzed four-component reaction. Apart from one molecule of water and the sodium counterion of the sulfinate, all atoms of the starting materials are transferred to the final product, rendering this process highly atom-efficient. The operationally simple protocol allows for the simultaneous formation of three new single bonds (C–S, C–N, and C–C) and therefore grants rapid access to structurally diverse products. The reaction proceeds under mild conditions in aqueous acetonitrile and shows a broad scope, including natural products and dru…

Flavans and other chemical constituents of Crinum biflorum (Amaryllidaceae)

Abstract The ethyl acetate extract from the whole plant of Crinum biflorum Rottb. Showed a moderate activity against Enterococcus faecalis. Its phytochemical investigation led to the isolation of a new flavan-3-ol derivative namely (2R,3R)-3-hydroxy-7-methoxy-3′,4′-methylenedioxyflavan, together with (2S)-7-hydroxy-3′,4′-methylenedioxyflavan, (2R,3R)-7-methoxy-flavan-3-ol, (2S)-7-hydroxy-3′,4′-dimethoxyflavan, 3′,7-dihydroxy-4′-methoxyflavan, 4′,7-dimethoxy-3′-hydroxyflavan, farrerol, β-sitosterol, β-sitosterol-3-O-β-D-glucopyranoside, oleanolic acid, kaempferol, pancratistatin, lupeol, aurantiamide acetate, Narciprimine and 2,3-dihydroxypropyl palmitate. Their structures were elucidated ma…

Applications of xylochemistry from laboratory to industrial scale

Xylochemicals and their utilisation in total synthesis and industrial applications are highlighted in this review. This class of chemicals consists of bio-based molecules or building blocks derived from renewable feedstocks like plant-biomass, lignocellulose as well as waste-streams. The advantages over petroleum-based chemicals are presented with the aid of specific examples ranging from the total synthesis of natural products, relevant industrial applications to the exploitation of CO2 as a C1 feedstock. This review contributes to the trend of a “greener” and a more sustainable chemistry.

Chemical constituents from Anthocleista liebrechtsiana De Wild & T. Durand (Loganiaceae)

Abstract A new steroid derivative, (24S)-3β-hydroxy-7β-methoxyergost-5-ene (1), was isolated along with eleven known compounds: 7α-hydroxysterol (2), β-sitosterol (3), oleanolic acid (4), betulinic acid (5), lupeol (6), swertiaperennin (7), decussatin (8), tetracosanoic acid (9) β-sitosterol-3-O-β- d -glucopyranoside (10), (2R,3S)-2,3-dihydro-2-(3,4-dimethoxyphenyl)-3-hydroxymethyl-5-(2-formylvinyl)-7-hydroxybenzofuran (11) and acacetin 6-C-β- d -glucopyranoside (12) from the tree bark and leaves of Anthocleista liebrechtsiana De Wild & T. Durand. Their structures were elucidated on the basis of spectroscopic (1D and 2D NMR) and mass spectrometric data. Compounds 2 and 7–10 have already bee…

A new ursane-type triterpene oxoglucopyranoside from Crossopteryx febrifuga.

Abstract A new saponin, 3-O-β-d-3-oxo-glucopyranosyl-ursa-12,20(30)-diene-27,28-dioic acid (1), was isolated from the methanol extract of stem bark of Crossopteryx febrifuga together with the known 3β-d-glucopyranosyl-ursa-12,20(30)-diene-27,28-dioic acid (2), shanzhiside methyl ester (3), shanzhiside (4), β-sitosterol (5), β-sitosterol-3-O-β-d-glucopyranoside (6), ursa-12,20(30)-diene-27,28-dioic acid (7), hederagenin (8), and oleanolic acid (9). The structures were established by comprehensive interpretation of their spectral data 1D- (1H and 13C), 2D-NMR (1H-1H COSY, HMQC, HMBC), spectroscopic, and electrospray ionisation time-of-flight mass spectrometry analysis. The isolated compounds …

Visible Light-Induced Sulfonylation/Arylation of Styrenes in a Double Radical Three-Component Photoredox Reaction

Simultaneous sulfonylation/arylation of styrene derivatives is achieved in a photoredox-catalyzed three-component reaction using visible light. A broad variety of difunctionalized products is accessible in mostly excellent yields and high diastereoselectivity. The developed reaction is scalable and suitable for the modification of styrene-functionalized biomolecules. Mechanistic investigations suggest the transformation to be operating through a designed sequence of radical formation and radical combination.

Antimicrobial secondary metabolites from the medicinal plant Crinum glaucum A. Chev. (Amaryllidaceae)

Abstract Medicinal plants are known as sources of potential antibacterial compounds including alkaloids. The aim of the present study was to evaluate the antibacterial activities of the extract, fractions, and some secondary metabolites isolated from the leaves of Crinum glaucum A. Chev. (Amaryllidaceae). The antibacterial activities were performed with the ethanol (EtOH) extract, as well as with ethyl acetate (EtOAc) and n-butanol (n-BuOH) fractions. Repeated column chromatography of the fractions led to the isolation of several compounds and their structures were elucidated mainly by means of extensive spectroscopic analysis [(one-dimensional (1D) and two-dimensional (2D) nuclear magnetic…

Hantzsch Ester-Mediated Photochemical Transformations in the Ketone Series: Remote C(sp3)–H Arylation and Cyclopentene Synthesis through Strain Release

A metal-free Hantzsch ester-mediated synthesis of cyclopentenylketones as well as γ-hetarylketones starting from ketocyclopropanes under eco-friendly conditions was developed. The versatility of the developed conditions is shown by reacting ketocyclopropanes in both a formal [3 + 2] cycloaddition with terminal alkynes (further investigated using theoretical calculations) and a radical C-C-coupling with cyanopyridines. The newly developed methodologies were later on utilized as a downstream reaction for photogenerated cyclopropanes combining UV and visible light photochemistry. Following this procedure, a UV-driven Norrish-Yang-type reaction induces the ring strain of the intermediates, whic…

Photoredox-Catalyzed Four-Component Reaction for the Synthesis of Complex Secondary Amines.

The one-pot sulfonylation/aminoalkylation of styrene derivatives furnishing substituted γ-sulfonylamines was accomplished through a photoredox-catalyzed four-component reaction. Besides one molecule of water and the sodium counterion of the sulfinate, all atoms of the starting materials are transferred to the final product, rendering this process highly atom-efficient. The operationally simple protocol allows for the simultaneous formation of three new single bonds (C-S, C-N, and C-C) and therefore grants rapid access to structurally diverse products.

Valorisation of Cashew Nut Shell Liquid Phenolics in the Synthesis of UV Absorbers

Front Cover: Valorisation of Cashew Nut Shell Liquid Phenolics in the Synthesis of UV Absorbers (Eur. J. Org. Chem. 30/2019)

Hepatoprotective effects of extracts, fractions and compounds from the stem bark of Pentaclethra macrophylla Benth: Evidence from in vitro and in vivo studies

Abstract Aim To identify the bioactive hepatoprotective components of the ethanol extract of Pentaclethra macrophylla stem bark using in vitro and in vivo approaches. Methods The bioguided-fractionation of the ethanol extract was based on the substances’ capacity to prevent in vitro, the lipid peroxidation of hepatocytes’ membranes induced by hydrogen peroxide. For the in vivo hepatoprotective test, mice were treated orally with the ethyl acetate (EtOAc) fraction of the ethanol extract at doses of 50 and 75 mg/kg/day for one week and subjected to d -galactosamine/lipopolysaccharide (GaIN/LPS)-induced hepatotoxicity. Blood samples were collected for alanine aminotransferase (ALAT), aspartate…

Examples of xylochemistry: colorants and polymers

Against the backdrop of modern sustainable chemistry and valorization of biomass for chemical raw materials, the syntheses of indigo dyes and polyamides as representatives of two classes of everyday chemical products based on xylochemicals are described. Wood-derived starting materials were transformed into functional materials using the principles of green chemistry to expand the scope of products gained from renewable resources. The indigo dyes were synthesized in a short, straightforward sequence starting from vanillin. Two polyamides, representatives of an important class of polymers, were obtained from 4-propylcyclohexanol, which is one of the longest known (and most abundant) hydrogen…

Cover Feature: Visible Light‐Induced Sulfonylation/Arylation of Styrenes in a Double Radical Three‐Component Photoredox Reaction (Chem. Eur. J. 38/2019)

Mimonoside D: a new triterpenoid saponin from Mimosa diplotricha Sauvalle (Fabaceae)

A new triterpenoid saponin (Mimonoside D: 3-O-��-L-arabinopyranosyl-3��-hydroxyolean-12-en-28-oic acid 28-O-��-D-xylopyranosyl-(1���2)-��-D- glucopyranoside ester (1)) was isolated from the aerial parts of Mimosa diplotricha Sauvalle together with nine known compounds: 7,4���-dihydroxyflavone (2), kaempferol (3), lupeol (4), betulinic acid (5), ��-sitosterol (6), ��-sitosterol-3-O-��-D-glucopyranoside (7), lutein (8), 5,2���-dihydroxy-7,4���,5���-trimethoxyflavone (9) and vitexin (10). Their structures were elucidated on the basis of spectroscopic (1 D and 2 D nuclear magnetic resonance) and high-resolution mass spectrometric data as well as by comparison of their spectral data with those o…

CCDC 1891336: Experimental Crystal Structure Determination

Related Article: Benjamin Lipp, Lisa Marie Kammer, Murat Kücükdisli, Adriana Luque, Jonas Kühlborn, Stefan Pusch, Gita Matulevičiūtė, Dieter Schollmeyer, Algirdas Šačkus, Till Opatz|2019|Chem.-Eur.J.|25|8965|doi:10.1002/chem.201901175