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Scientific Reports Jan 2020Diallyl disulfide (DADS) and allyl methyl sulfide (AMS) have been known as a metabolic product of sulfur-containing foods, typically garlic. The odour of such...
Diallyl disulfide (DADS) and allyl methyl sulfide (AMS) have been known as a metabolic product of sulfur-containing foods, typically garlic. The odour of such organosulfur compounds following garlic ingestion is often considered as an unpleasant element. Although previous studies have identified the DADS and AMS associated with garlic breath, no study has been reported on the determination of both compounds emanating from human skin surface. This study aimed to demonstrate the effect of garlic ingestion on the dermal emissions of DADS and AMS using a passive flux sampler coupled with gas chromatography-mass spectrometry. Firstly, baseline levels were investigated for 30 healthy volunteers in their daily life. The results of 1 h-sampling at the forearm showed the emission fluxes of both compounds followed the lognormal distribution with a geometric mean of 0.18 ng cm h for DADS and 0.22 ng cm h for AMS. Subsequently, the garlic ingestion tests were conducted for selected volunteers. The emission flux of DADS increased just after grilled garlic ingestion and decreased gradually thereafter. In contrast, the dermal emission flux of AMS reached a peak at 30 min after ingestion, and then gradually decreased. This peak shift suggests AMS is relatively latent in the skin organs.
Topics: Allyl Compounds; Cooking; Disulfides; Eating; Garlic; Gas Chromatography-Mass Spectrometry; Humans; Odorants; Skin; Sulfides; Surface Properties
PubMed: 31949194
DOI: 10.1038/s41598-019-57258-1 -
Journal of the American Chemical Society Apr 2016The enantioselective, intermolecular hydroallylation of vinylarenes employing allylic phosphate electrophiles has been achieved through a copper hydride catalyzed...
The enantioselective, intermolecular hydroallylation of vinylarenes employing allylic phosphate electrophiles has been achieved through a copper hydride catalyzed process. The protocol described herein can be applied to a diverse set of vinylarene substrates and allows for the installation of the parent allyl group as well as a range of 2-substituted allylic fragments.
Topics: Allyl Compounds; Benzene Derivatives; Catalysis; Copper; Styrene; Vinyl Compounds
PubMed: 27042864
DOI: 10.1021/jacs.6b02527 -
Viruses Jun 2017Dengue virus (DENV) is a mosquito-borne flavivirus that causes significant global human disease and mortality. One approach to develop treatments for DENV infection and...
Dengue virus (DENV) is a mosquito-borne flavivirus that causes significant global human disease and mortality. One approach to develop treatments for DENV infection and the prevention of severe disease is through investigation of natural medicines. Inflammation plays both beneficial and harmful roles during DENV infection. Studies have proposed that the oxidative stress response may be one mechanism responsible for triggering inflammation during DENV infection. Thus, blocking the oxidative stress response could reduce inflammation and the development of severe disease. Garlic has been shown to both reduce inflammation and affect the oxidative stress response. Here, we show that the garlic active compounds diallyl disulfide (DADS), diallyl sulfide (DAS) and alliin reduced inflammation during DENV infection and show that this reduction is due to the effects on the oxidative stress response. These results suggest that garlic could be used as an alternative treatment for DENV infection and for the prevention of severe disease development.
Topics: Allyl Compounds; Anti-Inflammatory Agents; Antioxidants; Cell Line; Cysteine; Dengue Virus; Disulfides; Garlic; Host-Pathogen Interactions; Humans; Oxidative Stress; Sulfides
PubMed: 28644404
DOI: 10.3390/v9070159 -
Organic Letters Mar 2021Although substituted benzimidazoles are common substructures in bioactive small molecules, synthetic methods for their derivatization are still limited. Previously,...
Although substituted benzimidazoles are common substructures in bioactive small molecules, synthetic methods for their derivatization are still limited. Previously, several enantioselective allylation reactions of benzimidazoles were reported that functionalize the nucleophilic nitrogen atom. Herein we describe a reversal of this inherent selectivity toward -allylation by using electrophilic -OPiv benzimidazoles with readily available 1,3-dienes as nucleophile precursors. This CuH-catalyzed approach utilizes mild reaction conditions, exhibits broad functional-group compatibility, and exclusively forms the C2-allylated product with excellent stereoselectivity.
Topics: Allyl Compounds; Benzimidazoles; Catalysis; Copper; Molecular Structure; Polyenes; Stereoisomerism
PubMed: 33646778
DOI: 10.1021/acs.orglett.1c00306 -
Angewandte Chemie (International Ed. in... Nov 2020A copper-based complex that contains a sulfonate N-heterocyclic carbene ligand was first reported 15 years ago. Since then, these organometallic entities have proven to... (Review)
Review
A copper-based complex that contains a sulfonate N-heterocyclic carbene ligand was first reported 15 years ago. Since then, these organometallic entities have proven to be uniquely effective in catalyzing an assortment of enantioselective transformations, including allylic substitutions, conjugate additions, proto-boryl additions to alkenes, boryl and silyl substitutions, hydride-allyl additions to alkenyl boronates, and additions of boron-containing allyl moieties to N-H ketimines. In this review article, we detail the shortcomings in the state-of-the-art that fueled the development of this air stable ligand class, members of which can be prepared on multigram scale. For each reaction type, when relevant, the prior art at the time of the advance involving sulfonate NHC-Cu catalysts and/or subsequent key developments are briefly analyzed, and the relevance of the advance to efficient and enantioselective total or formal synthesis of biologically active molecules is underscored. Mechanistic analysis of the structural attributes of sulfonate NHC-Cu catalysts that are responsible for their ability to facilitate transformations with high efficiency as well as regio- and enantioselectivity are detailed. This review contains several formerly undisclosed methodological advances and mechanistic analyses, the latter of which constitute a revision of previously reported proposals.
Topics: Alkenes; Allyl Compounds; Boron Compounds; Catalysis; Coordination Complexes; Copper; Heterocyclic Compounds; Imines; Methane; Molecular Structure; Nitriles; Stereoisomerism; Sulfonic Acids
PubMed: 32364640
DOI: 10.1002/anie.202003755 -
Organic Letters Nov 2010Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Brønsted acids activate allyl dioxazaborolidines to generate reactive...
Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Brønsted acids activate allyl dioxazaborolidines to generate reactive allyl-transfer reagents in situ. These reagents add to aldehydes and ketones to generate the corresponding alcohols in good yields under mild conditions. The E- and Z-crotyl reagents react diastereoselectively with aldehydes and ketones to produce anti and syn adducts, respectively, a result consistent with a cyclic transition state (type I mechanism).
Topics: Acids; Aldehydes; Allyl Compounds; Aza Compounds; Ketones; Models, Molecular; Molecular Structure
PubMed: 20942379
DOI: 10.1021/ol1020515 -
Angewandte Chemie (International Ed. in... Jul 2019Herein, we report a modular synthetic route to linear and branched homoallylic amines that operates through a sequential one-pot Lewis base/transition-metal catalyzed... (Review)
Review
Herein, we report a modular synthetic route to linear and branched homoallylic amines that operates through a sequential one-pot Lewis base/transition-metal catalyzed allylic alkylation/Hofmann rearrangement strategy. This protocol is operationally trivial, proceeds from simple and easily prepared substrates and catalysts, and enables all aspects of regio- and stereoselectivity to be controlled through a conserved experimental protocol. Overall, the high levels of enantio-, regio-, and diastereoselectivity obtained, in concert with the ability to access orthogonally protected or free amines, render this a straightforward and effective approach for the preparation of useful enantioenriched homoallylic amines. We have also demonstrated the utility of the products in the context of pharmaceutical synthesis.
Topics: Alkylation; Allyl Compounds; Amines; Catalysis; Metals, Heavy; Molecular Structure; Stereoisomerism
PubMed: 31132203
DOI: 10.1002/anie.201905426 -
Molecules (Basel, Switzerland) Sep 2018In this study, the nutritional, functional, and chemical measurements of sensory attributes of different parts of wasabi, namely, leaf, petiole, and rhizome, were...
In this study, the nutritional, functional, and chemical measurements of sensory attributes of different parts of wasabi, namely, leaf, petiole, and rhizome, were investigated. Proximate composition analysis showed the presence of high amounts of carbohydrates in the rhizome and amino acid composition analysis confirmed high proportions of glutamic acid and aspartic acid in all three parts. While proximate composition showed low lipid content in wasabi, ω-3 fatty acids accounted for a high proportion (>44%) of the total lipids. Wasabi leaves had high vitamin C and total phenolic contents, and thus demonstrated antioxidant capacity. Allyl isothiocyanate, which gives wasabi its characteristic pungent taste, was identified by gas chromatography/mass spectrometry and an electronic nose. On an electronic tongue, wasabi leaves showed compounds associated with sourness and saltiness while the petiole had high content of compounds associated with sweetness and bitterness. This study provides basic data for the utilization of wasabi parts as food materials based on their nutritional, functional, and chemical measure of sensory attributes.
Topics: Allyl Compounds; Ascorbic Acid; Fatty Acids, Omega-3; Isocyanates; Plant Components, Aerial; Rhizome; Wasabia
PubMed: 30274347
DOI: 10.3390/molecules23102512 -
Frontiers in Cellular and Infection... 2021Diallyl disulfide (DADS), a garlic extract also known as allicin, has been reported to have numerous biological activities, including anticancer, antifungal, and...
Diallyl disulfide (DADS), a garlic extract also known as allicin, has been reported to have numerous biological activities, including anticancer, antifungal, and inflammation-inhibiting activities, among others. Although many studies have assessed whether DADS can treat infection , its function and the underlying mechanism are still not clear. Accumulated evidence has implicated the gut microbiota as an important factor in the colonization and invasion of . Thus, this study aimed to identify the mechanism by which DADS ameliorates dextran sulfate (DSS)-induced intestinal infection based on the systematic analysis of the gut microbiota and metabolomics in mice. Here, we determined the body weight, survival, colon length, histological score, and inflammatory cytokine levels in the serum and intestines of experimental mice. Fecal samples were collected for gut microbiota and metabolite analysis by 16S rRNA gene sequencing and LC-MS metabolomics, respectively. DADS significantly alleviated DSS-induced intestinal infection and altered the gut microbial community structure and metabolic profile in the mice. The abundances of some pathogenic bacteria, such as , , and , were notably decreased after treatment with DADS. In contrast, SCFA-producing bacteria, namely, , , and , greatly increased in number. The perturbance of metabolites in infectious mice was improved by DADS, with increases in secondary bile acids, arachidonic acid, indoles and their derivatives, which were highly related to the multiple differentially altered metabolic pathways, namely, bile secretion, arachidonic acid metabolism, and tryptophan metabolism. This study indicated that DADS could modulate gut microbiota and metabolites and protect the gut barrier to alleviate DSS-induced intestinal infection in mice. Moreover, this work might also provide novel insight into the treatment of infection using DADS.
Topics: Allyl Compounds; Animals; Candida albicans; Dextran Sulfate; Disulfides; Gastrointestinal Microbiome; Mice; RNA, Ribosomal, 16S
PubMed: 35071031
DOI: 10.3389/fcimb.2021.743454 -
Journal of the American Chemical Society Dec 2021The Overhauser effect (OE), commonly observed in NMR spectra of liquids and conducting solids, was recently discovered in insulating solids doped with the radical...
The Overhauser effect (OE), commonly observed in NMR spectra of liquids and conducting solids, was recently discovered in insulating solids doped with the radical 1,3-bisdiphenylene-2-phenylallyl (BDPA). However, the mechanism of polarization transfer in OE-DNP in insulators is yet to be established, but hyperfine coupling of the radical to protons in BDPA has been proposed. In this paper we present a study that addresses the role of hyperfine couplings via the EPR and DNP measurements on some selectively deuterated BDPA radicals synthesized for this purpose. Newly developed synthetic routes enable selective deuteration at orthogonal positions or perdeuteration of the fluorene moieties with H incorporation of >93%. The fluorene moieties were subsequently used to synthesize two octadeuterated BDPA radicals, 1,3-[α,γ-]-BDPA and 1,3-[β,δ-]-BDPA, and a BDPA radical with perdeuterated fluorene moieties, 1,3-[α,β,γ,δ-]-BDPA. In contrast to the strong positive OE enhancement observed in degassed samples of fully protonated -BDPA (ε ∼ +70), perdeuteration of the fluorenes results in a negative enhancement (ε ∼ -13), while selective deuteration of α- and γ-positions ( ∼ 5.4 MHz) in BDPA results in a weak negative OE enhancement (ε ∼ -1). Furthermore, deuteration of β- and δ-positions ( ∼ 1.2 MHz) results in a positive OE enhancement (ε ∼ +36), albeit with a reduced magnitude relative to that observed in fully protonated BDPA. Our results clearly show the role of the hyperfine coupled α and γ H spins in the BDPA radical in determining the dominance of the zero and double-quantum cross-relaxation pathways and the polarization-transfer mechanism to the bulk matrix.
Topics: Allyl Compounds; Deuterium; Fluorenes; Free Radicals; Magnetic Resonance Spectroscopy
PubMed: 34813311
DOI: 10.1021/jacs.1c09406