Stereoselective Halogenation in Natural Product Synthesis

Angewandte Chemie International Edition, Journal Year: 2016, Volume and Issue: 55(14), P. 4396 - 4434

Published: Feb. 2, 2016

At last count, nearly 5000 halogenated natural products have been discovered. In approximately half of these compounds, the carbon atom to which halogen is bound sp(3) -hybridized; therefore, there are an enormous number for stereocontrolled halogenation must be a critical component any synthesis strategy. this Review, we critically discuss methods and strategies used stereoselective introduction atoms in context product synthesis. Using successes past, also attempt identify gaps our technology that would aid products, as well existing not yet seen application complex molecule The chemistry described herein demonstrates again how continue provide inspiration advances chemical

Language: Английский

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Biological Activity of Recently Discovered Halogenated Marine Natural Products

Marine Drugs, Journal Year: 2015, Volume and Issue: 13(7), P. 4044 - 4136

Published: June 30, 2015

This review presents the biological activity—antibacterial, antifungal, anti-parasitic, antiviral, antitumor, antiinflammatory, antioxidant, and enzymatic activity—of halogenated marine natural products discovered in past five years. Newly examples that do not report activity are included.

Language: Английский

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Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

Angewandte Chemie International Edition, Journal Year: 2015, Volume and Issue: 54(52), P. 15642 - 15682

Published: Dec. 2, 2015

Although recent years have witnessed significant advances in the development of catalytic, enantioselective halofunctionalizations alkenes, related dihalogenation olefins to afford enantioenriched vicinal dihalide products remains comparatively underdeveloped. However, growing number complex natural bearing halogen atoms at stereogenic centers has underscored this critical gap synthetic chemist's arsenal. This Review highlights selectivity challenges inherent design processes, and formulates a mechanism-based classification alkene dihalogenations, including those that may circumvent "classical" haliranium (or alkene-dihalogen π-complex) intermediates. A variety metal main group halide reagents been used for dichlorination or dibromination alkenes are discussed, proposed mechanisms these transformations critically evaluated.

Language: Английский

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A Survey of Recently Discovered Naturally Occurring Organohalogen Compounds

Journal of Natural Products, Journal Year: 2024, Volume and Issue: 87(4), P. 1285 - 1305

Published: Feb. 20, 2024

The discovery of naturally occurring organohalogen compounds has increased astronomically in the 55 years since they were first discovered─from fewer than 50 1968 to a combined 7,958 described examples three comprehensive reviews. present survey, which covers period 2021–2023, brings number known natural organohalogens approximately 8,400. organization is according species origin, and coverage includes marine terrestrial plants, fungi, bacteria, sponges, corals, cyanobacteria, tunicates, other organisms.

Language: Английский

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Unraveling the molecular basis of substrate specificity and halogen activation in vanadium-dependent haloperoxidases

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 28, 2025

Abstract Vanadium-dependent haloperoxidases (VHPOs) are biotechnologically valuable and operationally versatile biocatalysts. VHPOs share remarkable active-site structural similarities yet display variable reactivity selectivity. The factors dictating substrate specificity and, thus, a general understanding of VHPO reaction control still need to be discovered. This work’s strategic single-point mutation in the cyanobacterial bromoperoxidase Am facilitates selectivity switch allow aryl chlorination. induces loop formation that interacts with neighboring protein monomer, creating tunnel active sites. Structural analysis substrate-R425S-mutant complex reveals substrate-binding site at interface two adjacent units. There, residues Glu139 Phe401 interact arenes, extending residence time close vanadate cofactor stabilizing intermediates. Our findings validate long-debated existence direct binding provide detailed mechanistic understanding. work will pave way for broader application diverse chemical processes.

Language: Английский

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Photoinduced copper-catalysed deracemization of alkyl halides

Nature, Journal Year: 2025, Volume and Issue: 640(8057), P. 107 - 113

Published: April 2, 2025

Language: Английский

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Nontargeted Screening of Halogenated Organic Compounds in Bottlenose Dolphins (Tursiops truncatus) from Rio de Janeiro, Brazil

Environmental Science & Technology, Journal Year: 2017, Volume and Issue: 51(3), P. 1176 - 1185

Published: Jan. 5, 2017

To catalog the diversity and abundance of halogenated organic compounds (HOCs) accumulating in high trophic marine species from southwestern Atlantic Ocean, tissue bottlenose dolphins (Tursiops truncatus) stranded or incidentally captured along coast Rio de Janeiro, Brazil, were analyzed by a nontargeted approach based on GC×GC/TOF-MS. A total 158 individual HOCs 32 different structural classes detected blubber 4 adult male T. truncatus. Nearly 90% are not routinely monitored environment. DDT-related mirex/dechlorane-related most abundant anthropogenic origin. Methoxy-brominated diphenyl ethers (MeO-BDEs) chlorinated methyl- dimethyl bipyrroles (MBPs DMBPs) natural products. Reported for first time cetaceans contrast to North American mammals, MBPs DMBPs more than their brominated and/or mixed counterparts. HOC profiles coastal truncatus Brazil California revealed distinct difference, with higher MeO-BDEs, mirex/dechloranes Brazilian dolphins. Thirty-six percent had an unknown structure. These results suggest broad geographical differences patterns bioaccumulative chemicals found environment indicate need develop complete catalogs various environments.

Language: Английский

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Biological Activity and Structural Diversity of Steroids Containing Aromatic Rings, Phosphate Groups, or Halogen Atoms

Molecules, Journal Year: 2023, Volume and Issue: 28(14), P. 5549 - 5549

Published: July 20, 2023

This review delves into the investigation of biological activity and structural diversity steroids related isoprenoid lipids. The study encompasses various natural compounds, such as with aromatic ring(s), steroid phosphate esters derived from marine invertebrates, incorporating halogen atoms (I, Br, or Cl). These compounds are either produced by fungi fungal endophytes found in extracts plants, algae, invertebrates. To assess these an extensive examination referenced literature sources was conducted. evaluation encompassed vivo vitro studies, well utilization QSAR method. Numerous exhibited notable properties strong anti-inflammatory, anti-neoplastic, anti-proliferative, anti-hypercholesterolemic, anti-Parkinsonian, diuretic, anti-eczematic, anti-psoriatic, other activities. Throughout review, 3D graphs illustrating individual presented alongside images selected terrestrial organisms. Additionally, provides explanations for specific types associated compounds. data this hold scientific interest academic science practical implications fields pharmacology medicine. analysis lipids valuable insights that can contribute to advancements both theoretical understanding applied research.

Language: Английский

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Fluoride induces pyroptosis via IL-17A-mediated caspase-1/11-dependent pathways and Bifidobacterium intervention in testis

The Science of The Total Environment, Journal Year: 2024, Volume and Issue: 926, P. 172036 - 172036

Published: March 28, 2024

Language: Английский

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Update of the risk assessment of brominated phenols and their derivatives in food

EFSA Journal, Journal Year: 2024, Volume and Issue: 22(10)

Published: Oct. 1, 2024

Abstract The European Commission asked EFSA to update its 2012 risk assessment on brominated phenols and their derivatives in food, focusing five bromophenols one derivative: 2,4,6‐tribromophenol (2,4,6‐TBP), 2,4‐dibromophenol (2,4‐DBP), 4‐bromophenol (4‐BP), 2,6‐dibromophenol (2,6‐DBP), tetrabrominated bisphenol S (TBBPS), tetrabromobisphenol bismethyl ether (TBBPS‐BME). Based the overall evidence, CONTAM Panel considered vivo genotoxicity of 2,4,6‐TBP be unlikely. Effects liver kidney were as critical effects (2,4,6‐TBP) studies rats. A BMDL10 353 mg/kg body weight (bw) per day for papillary necrosis male rats was identified selected reference point characterisation. derivation a health‐based guidance value not appropriate due major limitations toxicological database. Instead, margin exposure (MOE) approach applied assess possible health concerns. Around 78,200 analytical results food used estimate dietary population. Considering resulting MOE values, all far above an 6000 that does raise concern, accounting uncertainties affecting hazard assessments, concluded with at least 95% probability current concern. Due lack occurrence data, no could performed breastfed or formula‐fed infants. No characterisation any other included assessment, data both toxicity occurrence.

Language: Английский

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