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Chemistry (Weinheim An Der Bergstrasse,... Apr 2015This Minireview discusses catalytic asymmetric conjugate addition and allylic alkylation reactions where the nucleophiles were generated in situ by hydrometallation or... (Review)
Review
This Minireview discusses catalytic asymmetric conjugate addition and allylic alkylation reactions where the nucleophiles were generated in situ by hydrometallation or carbometallation. This exciting recent trend in asymmetric catalysis promises to expand the range of transformations available for the rapid and selective assembly of complex, functional molecules for both academic and industrial research. This Minireview aims to serve as a reference for studies reported to date and discusses the current state-of-the-art, scope and limitations of these processes.
Topics: Alkylation; Allyl Compounds; Catalysis; Chemistry Techniques, Synthetic; Metals; Stereoisomerism
PubMed: 25603764
DOI: 10.1002/chem.201405855 -
Chemical Reviews Aug 2008
Review
Topics: Allyl Compounds; Catalysis; Copper; Molecular Structure; Stereoisomerism
PubMed: 18671436
DOI: 10.1021/cr0683515 -
International Journal of Peptide and... Oct 1993Allyl and allyloxycarbonyl groups are used for the side-chain protection of amino acids. The protecting groups may be selectively cleaved using the reagent HSnBu3 under...
Allyl and allyloxycarbonyl groups are used for the side-chain protection of amino acids. The protecting groups may be selectively cleaved using the reagent HSnBu3 under palladium catalysis. The preparation of Boc and Fmoc series of protected amino acids is described.
Topics: Allyl Compounds; Amino Acids; Palladium; Trialkyltin Compounds
PubMed: 8244630
DOI: 10.1111/j.1399-3011.1993.tb00504.x -
Organic & Biomolecular Chemistry Aug 2017A 3,4-disubstituted pyrrolidine ring was effectively cyclized through SmI-mediated reductive coupling between allyl chloride and an α,β-unsaturated ester, although...
A 3,4-disubstituted pyrrolidine ring was effectively cyclized through SmI-mediated reductive coupling between allyl chloride and an α,β-unsaturated ester, although little has been reported about SmI-promoted C-C bond formation of an allyl chloride with an α,β-unsaturated ester. Selection of either the 3,4-cis- or 3,4-trans-selective cyclization can be accomplished simply by changing the additives from NiI to HMPA during reductive cyclization conducted in HO-THF. Total synthesis of (-)-kainic acid and (+)-allo-kainic acid, which are pyrrolidine alkaloids used in neuroscience and neuropharmacology as useful molecular probes, was successfully achieved by using the stereo-complementary ring closure reactions promoted by SmI for the construction of the 2,3,4-trisubsituted pyrrolidine scaffold of kainoids.
Topics: Allyl Compounds; Cyclization; Esters; Iodides; Kainic Acid; Oxidation-Reduction; Samarium
PubMed: 28748237
DOI: 10.1039/c7ob01427a -
Journal of Economic Entomology Oct 1972
Topics: Allyl Compounds; Animals; Diptera; Female; Male; Ovum; Plants; Sex Factors; Thiocyanates
PubMed: 5085791
DOI: 10.1093/jee/65.5.1343 -
Nutrition and Health Jun 2022Therapy resistance is the underlying reason for poor outcome in prostate cancer (PCa) patients. Diallyl trisulfide (DATS) is an organosulfur compound present in garlic....
BACKGROUND
Therapy resistance is the underlying reason for poor outcome in prostate cancer (PCa) patients. Diallyl trisulfide (DATS) is an organosulfur compound present in garlic. DATS has been shown to target PCa cells by induction of apoptosis, increase in the production of reactive oxygen species, degradation of ferritin protein and increase in the labile iron (Fe) pool.
AIM
We hypothesize that DATS could induce ferroptosis, an Fe-dependent, unique non-apoptotic form of regulated cell death to eliminate therapy resistance encountered by PCa patients.
METHODS
and studies should be performed to test the hypothesis.
RESULTS
As per the hypothesis, DATS would eliminate apoptotic resistance via inducing ferroptosis.
CONCLUSION
Since apoptosis resistance has been reported to be the underlying mechanism of therapy resistance in PCa, DATS could be used to effectively target PCa cells by overcoming apoptosis resistance and inducing ferroptosis-mediated cell death of PCa cells.
Topics: Allyl Compounds; Antioxidants; Ferroptosis; Garlic; Humans; Male; Prostatic Neoplasms; Sulfides
PubMed: 34044656
DOI: 10.1177/02601060211018360 -
Talanta Dec 2019Pd-mediated Tsuji-Trost reaction is a practical strategy to design fluorescent probes for carbon monoxide (CO) sensing, and in such reaction CO can reduce Pd to Pd...
Pd-mediated Tsuji-Trost reaction is a practical strategy to design fluorescent probes for carbon monoxide (CO) sensing, and in such reaction CO can reduce Pd to Pd in-situ and remove allyl groups on fluorophores. In most of these probes, esters are commonly used to link allyl on fluorophores. We found that the ester groups could be hydrolyzed by esterase activity of fetal bovine serum (FBS), while FBS is a requisite in cell culture, and the hydrolysis could interfere the Pd-mediated Tsuji-Trost reaction. In this study, we synthesized a fluorescent probe (Cou-CO) using allyl ether as reaction site rather than allyl ester. Cou-CO is non-fluorescence, and could react with CO under the presence of Pd to form Cou with strong fluorescence, and the maximum excitation and emission wavelengths of Cou are 464 nm and 495 nm respectively. Cou-CO shows excellent selectivity to CO and could avoid the effect of FBS with the limit of detection for CO is 78 nm. Finally, Cou-CO was successfully applied for imaging of CO in living cells.
Topics: Allyl Compounds; Carbon Monoxide; Esters; Ethers; Fluorescent Dyes; HeLa Cells; Humans; Limit of Detection; Molecular Imaging; Onions; Sensitivity and Specificity; Serum Albumin, Bovine
PubMed: 31450480
DOI: 10.1016/j.talanta.2019.06.070 -
Organic & Biomolecular Chemistry Mar 2008The chain-breaking antioxidant activities of two garlic-derived allyl sulfides, i.e. diallyl disulfide (1), the main component of steam-distilled garlic oil, and allyl...
The chain-breaking antioxidant activities of two garlic-derived allyl sulfides, i.e. diallyl disulfide (1), the main component of steam-distilled garlic oil, and allyl methyl sulfide (3) were evaluated by studying the thermally initiated autoxidation of cumene or styrene in their presence. Although the rate of cumene oxidation was reduced by addition of both 1 and 3, the dependence on the concentration of the two sulfides could not be explained on the basis of the classic antioxidant mechanism as with phenolic antioxidants. The rate of oxidation of styrene, on the other hand, did not show significant changes upon addition of either 1 or 3. This unusual behaviour was explained in terms of the co-oxidant effect, consisting in the decrease of the autoxidation rate of a substrate forming tertiary peroxyl radicals (i.e. cumene) upon addition of little amounts of a second oxidizable substrate giving rise instead to secondary peroxyl radicals. The relevant rate constants for the reaction of ROO(.) with 1 and 3 were measured as 1.6 and 1.0 M(-1) s(-1), respectively, fully consistent with the H-atom abstraction from substituted sulfides. It is therefore concluded that sulfides 1 and 3 do not scavenge peroxyl radicals and therefore cannot be considered chain-breaking antioxidants.
Topics: Allyl Compounds; Benzene Derivatives; Free Radical Scavengers; Free Radicals; Garlic; Kinetics; Molecular Structure; Oxidation-Reduction; Peroxides; Styrene; Sulfides
PubMed: 18327338
DOI: 10.1039/b719348c -
Angewandte Chemie (International Ed. in... Nov 2022We describe cooperative bimetallic catalysis that enables regio-/stereodivergent asymmetric α-allylations of aldimine esters. By employing Et B as the key activator,...
Cooperative Catalyst-Enabled Regio- and Stereodivergent Synthesis of α-Quaternary α-Amino Acids via Asymmetric Allylic Alkylation of Aldimine Esters with Racemic Allylic Alcohols.
We describe cooperative bimetallic catalysis that enables regio-/stereodivergent asymmetric α-allylations of aldimine esters. By employing Et B as the key activator, racemic allylic alcohols can be directly ionized to form Pd or Ir-π-allyl species in the presence of achiral Pd or chiral Ir complexes, respectively. The less or more substituted allylic termini of the metal-π-allyl species are amenable to nucleophilic attack by the chiral Cu-azomethine ylide, the formation of which is simultaneously facilitated by Et B, affording α-quaternary α-amino acids with high regioselectivity and excellent stereoselectivity. The use of readily available allylic alcohols as electrophilic precursors represents an improvement from an environmental and atom/step economy perspective. Computational mechanistic studies reveal the crucial role of the Et B additive and the origins of stereo- and regioselectivities by analyzing steric effects, dispersion interactions, and frontier orbital population.
Topics: Esters; Stereoisomerism; Allyl Compounds; Molecular Structure; Alkylation; Catalysis; Amino Acids
PubMed: 36161447
DOI: 10.1002/anie.202212948 -
Archives of Toxicology 1987Allylic compounds exert direct genotoxic activities which depend on the chemical nature of the leaving group and on further substituents. Besides the direct genotoxic...
Allylic compounds exert direct genotoxic activities which depend on the chemical nature of the leaving group and on further substituents. Besides the direct genotoxic effects, metabolic activation mechanisms are also conceivable. Epoxidation seems to play a minor role in bioactivation, whereas the metabolic formation of strongly mutagenic alpha, beta-unsaturated carbonyl compounds is obviously of great importance for the indirect genotoxicity of allylic compounds. Only in the case of 2,3-dichloro-1-propene is an epoxide formed which is extremely unstable and immediately rearranges to the strong mutagen, 1,3-dichloroacetone.
Topics: Allyl Compounds; Animals; Biotransformation; DNA; HeLa Cells; Humans; In Vitro Techniques; Mutagenicity Tests; Mutagens; Rats
PubMed: 3619639
DOI: 10.1007/BF00296977