- Natural trienoic acids as anticancer agents: First stereoselective synthesis, cell cycle analysis, induction of apoptosis, cell signaling and mitochondrial targeting studies
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The first Z-stereoselective method was developed for the synthesis of unsaturated acids containing a 1Z,5Z,9Z-triene moiety in 61–64% yields using the new Ti-catalyzed cross-coupling of oxygen-containing and aliphatic 1,2-dienes as the key synthetic step. It was shown for the first time that trienoic acids with non-methylene-interrupted Z-double bonds show moderate cytotoxic activities against tumor cell lines (Jurkat, K562, U937, HL60, HeLa), human embryonic kidney cells (Hek293), normal fibroblasts and human topoisomerase I (hTop1) inhibitory activity in vitro. The synthesized acids efficiently initiate apoptosis of Jurkat tumor cells, with the cell death mechanism being activated by the mitochondrial pathway. A probable mechanism of topoisomerase I inhibition was also hypothesized on the basis of in silico studies resorting to docking. The activation and inhibition of the most versatile intracellular signaling pathways (CREB, JNK, NFkB, p38, ERK1/2, Akt, p70S6K, STAT3 and STAT5 tyrosine kinases) responsible for cell proliferation and for initiation of apoptosis were studied by multiplex assay technology (Luminex xMAP).
- D’yakonov, Vladimir A.,Makarov, Alexey A.,Dzhemileva, Lilya U.,Ramazanov, Ilfir R.,Makarova, Elina Kh.,Dzhemilev, Usein M.
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- Sustainable, mild and efficient p-methoxybenzyl ether deprotections utilizing catalytic DDQ
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A procedure for the selective deprotection of p-methoxybenzyl ethers using catalytic amounts of DDQ and of sodium nitrite, with oxygen as the terminal oxidant, is reported.
- Walsh, Katie,Sneddon, Helen F.,Moody, Christopher J.
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p. 7380 - 7387
(2017/09/13)
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- Platinum-catalyzed hydrosilylations of internal alkynes: Harnessing substituent effects to achieve high regioselectivity
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Rule of thumb: The high yielding title reaction is described with a focus on understanding the factors that govern the regioselectivity of the process (see scheme). Electronic, steric, and functional group properties all influence the selectivity, an understanding of which allows the selective formation of trisubstituted vinylsilanes, which are synthetically useful compounds for accessing stereodefined alkenes. Copyright
- Rooke, Douglas A.,Ferreira, Eric M.
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supporting information; experimental part
p. 3225 - 3230
(2012/05/31)
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- Enzyme-triggered enantioconvergent transformation of haloalkyl epoxides
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Biocatalytic hydrolysis of 2,3-disubstituted rac-cis- and rac-trans-haloalkyl epoxides 1a-8a using the epoxide hydrolase activity of whole bacterial cells furnished the corresponding vicinal diols 1b-8b as intermediates; these (spontaneously) underwent ring closure to yield cyclic products 1c-6c through an enzyme-triggered cascade reaction. In particular, cis-configured substrates (1a, 3a, 5a, 7a) were transformed in an enantioconvergent fashion, which resulted in the formation of single stereoisomeric products in 100% des and up to 92% ees from the racemates.
- Mayer, Sandra F.,Steinreiber, Andreas,Orru, Romano V. A.,Faber, Kurt
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p. 4537 - 4542
(2007/10/03)
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- An enzyme-triggered enantio-convergent cascade-reaction
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The biocatalytic hydrolysis of the (±)-2,3-disubstituted cis-chloroalkyl epoxides 1a and 2a using resting cells of Rhodococcus sp. did not give the corresponding chloroalkyl vic-diols 1b, and 2b, respectively, but furnished the rearranged products (2R,3R)-1c and (2R,3R)-2c in high e.e. as the sole products via an enzyme-triggered enantio-convergent cascade-reaction.
- Mayer, Sandra F.,Steinreiber, Andreas,Orru, Romano V.A.,Faber, Kurt
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- Selective Cleavage of Dimethylhydrazones to the Carbonyl Compounds Using Silica Gel and its Application in the Synthesis of (Z)-9-Tetradecenyl Acetate
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A new method for the selective hydrolytic cleavage of dimethylhydrazones consists of treatment of the hydrazones with silica gel (pH 6.80) in wet tetrahydrofuran.Utilizing this method as one of the key steps, (Z)-9-tetradecenyl acetate, the pheromone of Spodoptera frugiperda, was synthesized.
- Mitra, R. B.,Reddy, G. Bhaskar
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p. 694 - 698
(2007/10/02)
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- Syntheses of Monounsaturated Sex Pheromones of Lepidoptera via 3-Alkyn-1-ols
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3-Alkyn-1-ols as intermediate synthons in the preparation of some Lepidoteran sex pheromones were utilized.Characteristic fragmentations reflecting the position of the triple bond were found in the mass spectra of 3-alkyn-1-ols and alkyn-1-yl acetates in contrast to 1-tert-butoxy-alkynes.A partial isomerization of 1-tosyloxy-3-(Z)-octene to 1-bromo-3-(E)-octene within the reaction with NaBr in DMF was noticed by GC and 13C-n.m.r., for which a mechanism involving homoconjugation in an intermediate non-classical carbonium ion was suggested.
- Pop, Lidia,Oprean, I.,Barabas, A.,Hodosan, F.
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p. 867 - 878
(2007/10/02)
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- INSECT PHEROMONES AND THEIR ANALOGS. XII. SYNTHESIS OF THE ISOMERIC DEC-5-ENYL ACETATES - THE SEX PHEROMONES OF Anarsia lineatella AND Agrotis segetum
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A new route for the synthesis of dec-5E- and -5Z-enyl acetates - the sex pheromones of the peach-tree borer and of the turnip moth - is proposed which is based on the two-stage hydroxyethylation of hex-1-yne using 2-chloroethyl vinyl ethers and ethylene oxide.
- Odinokov, V. N.,Balezina, G. G.,Ishmuratov, G. Yu.,Vakhitov, R. Sh.,Tolstikov, G. A.
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p. 369 - 371
(2007/10/02)
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