Alkyl Carbagermatrane Enabled Synthesis of Seven-Membered Carbocycle-Fused Aromatics through Catellani Strategy

Synthesis ◽  
2021 ◽  
Author(s):  
Xiu-Ying Xie ◽  
Wei-Tao Jiang ◽  
Bin Xiao
Keyword(s):  
Natural Product ◽  
Functional Groups ◽  
Bioactive Molecules ◽  
Intermolecular Cyclization

Synthesis of seven-membered carbocycle-fused aromatics was realized by Catellani reaction using terminally brominated alkyl carbagermatranes through intermolecular cyclization manner. Various functional groups were well tolerated, and this transformation was also expanded to the synthesis of carbocycles of other size. The utility of this method was demonstrated by modification of natural product derivatives and synthesis of bioactive molecules.

Reductive Cleavage of Secondary Sulfonamides: Converting Terminal Functional Groups into Versatile Synthetic Handles

2019 ◽  
Author(s):  
Patrick Fier ◽  
Suhong Kim ◽  
Kevin M. Maloney
Keyword(s):  
Functional Groups ◽  
Late Stage ◽  
Reductive Cleavage ◽  
Bioactive Molecules ◽  
General Method

Sulfonamides are pervasive in drugs and agrochemicals, yet are typically considered as terminal functional groups rather than synthetic handles. To enable the general late-stage functionalization of secondary sulfonamides, we have developed a mild and general method to reductively cleave the N-S bonds of sulfonamides to generate sulfinates and amines, components which can further react <i>in-situ</i> to access a variety of other medicinally relevant functional groups. The utility of this platform is highlighted by the selective manipulation of several complex bioactive molecules.

scholarly journals Synthesis of chiral anti-1,2-diamine derivatives through copper(I)-catalyzed asymmetric α-addition of ketimines to aldimines

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Xu-Cheng Gan ◽  
Cheng-Yuan Zhang ◽  
Feng Zhong ◽  
Ping Tian ◽  
Liang Yin
Keyword(s):  
Nitro Group ◽  
Functional Groups ◽  
Phenyl Group ◽  
Asymmetric Reactions ◽  
Bioactive Molecules ◽  
Sandmeyer Reaction ◽  
Aryl Amine ◽  
Common Structure ◽  
Group A ◽  
High Yields

Abstract Chiral 1,2-diamines serve as not only common structure units in bioactive molecules but also useful ligands for a range of catalytic asymmetric reactions. Here, we report a method to access anti-1,2-diamine derivatives. By means of the electron-withdrawing nature of 2- or 4-nitro-phenyl group, a copper(I)-catalyzed asymmetric α-addition of ketimines derived from trifluoroacetophenone and 2- or 4-NO2-benzylamines to aldimines is achieved, which affords a series of chiral anti-1,2-diamine derivatives in moderate to high yields with moderate to high diastereoselectivity and high to excellent enantioselectivity. Aromatic aldimines, heteroaromatic aldimines, and aliphatic aldimines serve as suitable substrates. The nitro group is demonstrated as a synthetical handle by several transformations, including a particularly interesting Fe(acac)3-catalyzed radical hydroamination with a trisubstituted olefin. Moreover, the aryl amine moiety obtained by the reduction of the nitro group serves as a synthetically versatile group, which leads to the generation of several functional groups by the powerful Sandmeyer reaction, such as -OH, -Br, -CF3, and -BPin.

Formal Total Synthesis of (±)-Rhazinal: Evaluating the Radical Approach

Synthesis ◽  
2017 ◽  
Vol 49 (11) ◽  
pp. 2584-2588 ◽  
Author(s):  
Sven Hildebrandt ◽  
Hendrik Weißbarth ◽  
Andreas Gansäuer
Keyword(s):  
Total Synthesis ◽  
Natural Product ◽  
Functional Groups ◽  
Radical Approach

We describe a formal total synthesis of the racemic natural product rhazinal by a rapid elaboration of a recently reported tetrahydroindolizine intermediate into the cyclization precursor reported by Trauner. The synthesis focuses on the early and convergent introduction of functional groups while the synthetic challenges encountered by this approach are described.

Nanocarriers as Administration Systems of Natural Products

2021 ◽  
Vol 21 ◽  
Author(s):  
Guadalupe Y. Solís-Cruz ◽  
Luis A. Pérez-López ◽  
Rocio Alvarez-Roman ◽  
Verónica M. Rivas-Galindo ◽  
David A. Silva-Mares ◽  
...  
Keyword(s):  
Natural Products ◽  
Natural Product ◽  
Drug Administration ◽  
Therapeutic Agents ◽  
Bioactive Molecules ◽  
Biological Applications

: Natural products are an important source of bioactive molecules. However, the development of biological applications based on these compounds is hindered by intrinsic problems in their solubility, volatility, degradation, and bioavailability. Nanocarriers as drug administration systems promise to overcome these limitations by providing controlled and directed delivery. This review aims to present: 1) the most frequently used nanocarriers as natural product administration systems, based on the progress of controlled and directed release, and 2) the challenges associated with the use of nanocarriers as therapeutic agents.

scholarly journals A Single Biosynthetic Gene Cluster Is Responsible for the Production of Bagremycin Antibiotics and Ferroverdin Iron Chelators

mBio ◽  
2019 ◽  
Vol 10 (4) ◽  
Author(s):  
Loïc Martinet ◽  
Aymeric Naômé ◽  
Benoit Deflandre ◽  
Marta Maciejewska ◽  
Déborah Tellatin ◽  
...  
Keyword(s):  
Natural Product ◽  
Gene Cluster ◽  
Biosynthetic Pathway ◽  
Genome Mining ◽  
Gene Clusters ◽  
Bioactive Molecules ◽  
Bioactive Metabolites ◽  
Biosynthetic Gene ◽  
Single Family ◽  
Biosynthetic Gene Clusters

ABSTRACT Biosynthetic gene clusters (BGCs) are organized groups of genes involved in the production of specialized metabolites. Typically, one BGC is responsible for the production of one or several similar compounds with bioactivities that usually only vary in terms of strength and/or specificity. Here we show that the previously described ferroverdins and bagremycins, which are families of metabolites with different bioactivities, are produced from the same BGC, whereby the fate of the biosynthetic pathway depends on iron availability. Under conditions of iron depletion, the monomeric bagremycins are formed, representing amino-aromatic antibiotics resulting from the condensation of 3-amino-4-hydroxybenzoic acid with p-vinylphenol. Conversely, when iron is abundantly available, the biosynthetic pathway additionally produces a molecule based on p-vinylphenyl-3-nitroso-4-hydroxybenzoate, which complexes iron to form the trimeric ferroverdins that have anticholesterol activity. Thus, our work shows a unique exception to the concept that BGCs should only produce a single family of molecules with one type of bioactivity and that in fact different bioactive molecules may be produced depending on the environmental conditions. IMPORTANCE Access to whole-genome sequences has exposed the general incidence of the so-called cryptic biosynthetic gene clusters (BGCs), thereby renewing their interest for natural product discovery. As a consequence, genome mining is the often first approach implemented to assess the potential of a microorganism for producing novel bioactive metabolites. By revealing a new level of complexity of natural product biosynthesis, we further illustrate the difficulty of estimation of the panel of molecules associated with a BGC based on genomic information alone. Indeed, we found that the same gene cluster is responsible for the production of compounds which differ in terms of structure and bioactivity. The production of these different compounds responds to different environmental triggers, which suggests that multiplication of culture conditions is essential for revealing the entire panel of molecules made by a single BGC.

scholarly journals Application of FT-IR Spectroscopy for Fingerprinting Bioactive Molecules in a Nutraceutical PROMEN, comparatively with Plantingredients

2013 ◽  
Vol 70 (1) ◽  
pp. 68
Author(s):  
Florina Csernatoni ◽  
Carmen Socaciu ◽  
Raluca Maria Pop ◽  
Florinela Fetea
Keyword(s):  
Ir Spectroscopy ◽  
Functional Groups ◽  
Food Supplement ◽  
Bioactive Molecules ◽  
Ft Ir ◽  
Fingerprint Region ◽  
Phenolic Derivatives ◽  
Ft Ir Spectroscopy

The aim of this study is to characterize and identify the main biomarkers of food supplement PROMEN by analysis of plant ingredients comparatively with the final product. Alcoholic extracts of plants were prepared at 15% plant content and purified fractions were analyzed by FTIR screening. The fingerprint region (1000 to 1500 cm-1) indicated the presence of specific functional groups to identify and monitor the phenolic derivatives.

scholarly journals Asymmetric Alkene and Arene Halofunctionalization Reactions in Meroterpenoid Biosynthesis

Synlett ◽  
2017 ◽  
Vol 29 (04) ◽  
pp. 401-409 ◽  
Author(s):  
Bradley Moore
Keyword(s):  
Natural Products ◽  
Natural Product ◽  
Bioactive Molecules ◽  
Broad Distribution ◽  
Rearrangement Reactions

Meroterpenoid natural products are important bioactive molecules with broad distribution throughout nature. In Streptomyces bacteria, naphthoquinone-based meroterpenoids comprise a simple yet structurally fascinating group of natural product antibiotics that are enzymatically constructed through a series of asymmetric alkene and arene halofunctionalization reactions. This account article highlights our discovery and characterization of a group of vanadium-dependent chloroperoxidase enzymes that catalyze halogen-assisted cyclization and rearrangement reactions and have inspired biomimetic syntheses of numerous meroterpenoid natural products.1 Introduction2 Early Biosynthetic Insights and the Characterization of Alkene Halofunctionalization in Napyradiomycin Biosynthesis3 Discovery of the Merochlorin Natural Products and Enzymatic Aryl Halofunctionalization4 Discovery and Development of Unifying THN-Based Meroterpenoid Biosynthesis and Synthesis Approaches5 Insights into Naphterpin and Marinone Biosynthesis Involving Cryptic Aryl Halofunctionalization Reactions6 Closing Thoughts

scholarly journals Reductive Cleavage of Secondary Sulfonamides: Converting Terminal Functional Groups into Versatile Synthetic Handles

2019 ◽  
Author(s):  
Patrick Fier ◽  
Suhong Kim ◽  
Kevin M. Maloney
Keyword(s):  
Functional Groups ◽  
Late Stage ◽  
Reductive Cleavage ◽  
Bioactive Molecules ◽  
General Method

Sulfonamides are pervasive in drugs and agrochemicals, yet are typically considered as terminal functional groups rather than synthetic handles. To enable the general late-stage functionalization of secondary sulfonamides, we have developed a mild and general method to reductively cleave the N-S bonds of sulfonamides to generate sulfinates and amines, components which can further react <i>in-situ</i> to access a variety of other medicinally relevant functional groups. The utility of this platform is highlighted by the selective manipulation of several complex bioactive molecules.

A Tandem Sulfonylation and Knoevenagel Condensation for the Preparation of Sulfocoumarin-3-carboxylates

Synthesis ◽  
2019 ◽  
Vol 51 (08) ◽  
pp. 1809-1818 ◽  
Author(s):  
Ziyang Dong ◽  
Yang Chen ◽  
Zhiheng Yang ◽  
Zhanhui Yang ◽  
Jiaxi Xu
Keyword(s):  
Functional Groups ◽  
Knoevenagel Condensation ◽  
Sulfonyl Chloride ◽  
Ester Group ◽  
Bioactive Molecules ◽  
One Pot ◽  
Structural Motifs ◽  
Phenolic Hydroxy

Sulfocoumarins are key structural motifs in several bioactive molecules. Herein, we describe a simple, one-pot procedure for the synthesis of structurally diverse sulfonocoumarin-3-carboxylates by heating 2-hydroxyaryl aldehydes with an active sulfonyl chloride in the presence of pyridine. The process tolerates numerous functional groups including alkoxy, alkyl, halogen, nitro, and even nucleophilic phenolic hydroxy. Additionally, reactions of 2-hydroxyaryl ketones and 2-methylaminoaryl aldehydes give 4-substituted sulfocoumarins and 1-aza-2-sulfocoumarins, respectively. A gram-scale synthesis and further derivatizations are also reported. The ester group is easily removed via ­Happer’s decarboxylation.

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