- A NEW APPROACH TO CONJUGATED DIENES SYNTHESIS OF THE PHEROMONES OF LOBESIA BOTRANA AND BOMBYX MORI
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Cis or trans epoxysilanes are regio and stereoselectively opened by Z-alkenyl cuprates, in the presence of BF3*OEt2, affording erythro or threo β-hydroxy silanes respectively.These are, in turn, transformed into E-Z conjugated dienes of high stereoisomeric purity by acidic or basic elimination.The method serves to synthetize the pheromones of Lobesia botrana and Bombyx mori.
- Alexakis, A.,Jachiet, D.
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- A 13-oxo-9,10-epoxytridecenoate phospholipid analogue of the genotoxic 4,5-epoxy-2E-decenal: Detection in vivo, chemical synthesis, and adduction with DNA
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Often guided by analogy with nonphospholipid products from oxidative cleavage of polyunsaturated fatty acids, we previously identified a variety of biologically active oxidatively truncated phospholipids. Previously, 4,5-epoxy-2(E)-decenal (4,5-EDE) was found to be produced by oxidative cleavage of 13-(S)-hydroperoxy-9,11-(Z,E)-octadeca-dienoic acid (13-HPODE). 4,5-EDE reacts with deoxy-adenosine (dAdo) and deoxy-guanosine (dGuo) to form mutagenic etheno derivatives. We hypothesized that a functionally similar and potentially mutagenic compound, that is, 13-oxo-9,10-epoxytridecenoic acid (OETA), would be generated from 9-HPODE through an analogous fragmentation. We expected that an ester of 2-lysophosphatidylcoline (PC), OETA-PC, would be produced by oxidative cleavage of 9-HPODEPC in biological membranes. An efficient, unambiguous total synthesis of trans-OETA-PC was first executed to provide a standard that could facilitate the identification of this phospholipid epoxyalkenal that was shown to be produced during oxidation of the linoleic acid ester of 2-lysoPC. Finally, trans-OETA-PC was detected in a lipid extract from rat retina. The identity of the naturally occurring oxidatively truncated phospholipid was further confirmed by derivatization with methoxylamine that produced characteristic mono and bis adducts. The average amount of trans-OETA-PC in rat retina, 0.33 pmol, is relatively low as compared to other oxidatively truncated PCs, for example, the 4-hydroxy-7-oxohept-5-enoic acid PC ester (2.5 pmol) or the 4-keto-7-oxohept-5- enoic acid PC ester (1.7 pmol), derived from the docosahexaenoic acid ester of 2-lysoPC. This, most likely, is because docosahexaenoate PCs are particularly abundant in the retina as compared to the linoleate PC ester precursor of OETA-PC. As predicted by analogy with 4,5-EDE, OETA-PC reacts with dAdo and dGuo, as well as with DNA, to form mutagenic etheno adducts.
- Mesaros, Clementina,Gugiu, Bogdan G.,Zhou, Rong,Lee, Seon Hwa,Choi, Jaewoo,Laird, James,Blair, Ian A.,Salomon, Robert G.
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Read Online
- Antibacterial Activity of Hexadecynoic Acid Isomers toward Clinical Isolates of Multidrug-Resistant Staphylococcus aureus
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In the present study, the structural characteristics that impart antibacterial activity to C16 alkynoic fatty acids (aFA) were further investigated. The syntheses of hexadecynoic acids (HDA) containing triple bonds at C-3, C-6, C-8, C-9, C-10, and C-12 were carried out in four steps and with an overall yield of 34–78%. In addition, HDA analogs containing a sulfur atom at either C-4 or C-5 were also prepared in 69–77% overall yields, respectively. Results from this study revealed that the triple bond at C-2 is pivotal for the antibacterial activity displayed by 2-HDA, while the farther the position of the triple bond from the carbonyl group, the lower its bactericidal activity against gram-positive bacteria, including clinical isolates of methicillin-resistant Staphylococcus aureus (CIMRSA) strains. The potential of 2-HDA as an antibacterial agent was also assessed in five CIMRSA strains that were resistant to Ciprofloxacin (Cipro) demonstrating that 2-HDA was the most effective treatment in inhibiting their growth when compared with either Cipro alone or equimolar combinations of Cipro and 2-HDA. Moreover, it was proved that the inhibition of S. aureus DNA gyrase can be linked to the antibacterial activity displayed by 2-HDA. Finally, it was determined that the ability of HDA analogs to form micelles can be linked to their decreased activity against gram-positive bacteria, since critical micellar concentrations (CMC) between 50 and 300 μg/mL were obtained.
- Carballeira, Néstor M.,Chorna, Nataliya,Díaz, Damarith,Medina, Solymar,Mooney, Joseph,Morales-Guzmán, Christian,Ocasio-Malavé, Carlimar,Pereles-De-León, Tomás,Rivera-Román, Ashley,Sanabria-Ríos, David J.
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- Practical Synthesis and Field Application of the Synthetic Sex Pheromone of Rice Stem Borer, Chilo suppressalis (Lepidoptera: Pyralidae)
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Rice stem borer, Chilo suppressalis, is a common and major serious pest of rice, maize, and wheat crops across Asia, Europe, and Oceania countries. Its sex pheromone consists of three analogously compounds, i.e., (Z)-hexadec-11-enal (1), (Z)-octadec-13-enal (2), and (Z)-hexadec-9-enal (3), as long-chain aliphatic internal cis-alkenyl aldehydes. In order to perform an economic and widespread pest control management of rice stem borer, a versatile and efficient synthetic strategy is required. A versatile and efficient synthesis using a common synthetic route for cis-alkenals with high overall yields is described. Commercially available inexpensive aliphatic diols were chosen as starting materials. Two key steps were employed to synthesize the long-chain aliphatic internal cis-alkenes in excellent yields, including the alkylation of terminal alkynes without the utilization of a highly polar aprotic cosolvent and the versatile cis-selective semihydrogenation for the reduction of internal alkynes with excellent stereoselectivity. The results of field tests showed that the synthetic sex pheromone blend was highly effective for the capture of rice stem borer.
- Chien, Wei-Jynn,Gupta, Sachin,Liu, Bin,Lou, Da Wei,Shen, Yu-Jhe,Syu, Kun-Jie,Tseng, Jui-Chang,Zhang, Yuan-Xin
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- Identification and synthesis of the male produced volatiles of the carrion beetle, Oxelytrum erythrurum (Coleoptera: Silphidae)
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Necrophagous beetles belonging to the family Silphidae are recognized as potentially useful in forensic investigations (to estimate post mortem interval). Gas chromatography analyses of extracts of aerations of adult Oxelytrum erythrurum revealed the presence of two male-specific compounds. These compounds were identified as (Z)-1,10-nonadecadiene (major) and 1-nonadecene (minor) using microderivatizations of the natural male extract, such as hydrogenation, partial reduction and methylthiolation, mass spectrum comparisons, and co-injections with authentic standards. Both compounds might be components of a pheromone responsible for sexual communication in this species.
- Fockink, Douglas H.,Martins, Camila B.C.,Zarbin, Paulo H.G.
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p. 5353 - 5356
(2015/09/01)
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- Synthesis of corn rootworm pheromones from commercial diols
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A mixture of stereoisomers of the corn rootworm pheromones was synthesised via the Grignard coupling of protected bromohydrins with alkylcuprate as a key step. The synthesis of 8-methyldec-2- yl propanoate (I), the northern corn rootworm Diabrotica longicornis Say pheromone, was achieved from pentane-1,5-diol in four steps with an overall yield of 35.1 % and 10-methyltridecan-2-one (II), the southern corn rootworm Diabrotica undecimpunctata howardi Barber pheromone, was synthesised from octane-1,8-diol as commercially available starting material in five steps with an overall yield of 28.7 %.
- Nguyen, Thanh-Danh,Nguyen, Cong-Hao,Im, Chan,Dang, Chi-Hien
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p. 380 - 384
(2015/02/19)
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- The (5Z)-5-Pentacosenoic and 5-Pentacosynoic Acids Inhibit the HIV-1 Reverse Transcriptase
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The natural fatty acids (5Z)-5-pentacosenoic and (9Z)-9-pentacosenoic acids were synthesized for the first time in eight steps starting from either 4-bromo-1-butanol or 8-bromo-1-butanol and in 20-58 % overall yields, while the novel fatty acids 5-pentacosynoic and 9-pentacosynoic acids were also synthesized in six steps and in 34-43 % overall yields. The ?5 acids displayed the best IC50's (24-38 μM) against the HIV-1 reverse transcriptase (RT) enzyme, comparable to nervonic acid (IC50 = 12 μM). The ?9 acids were not as effective towards HIV-RT with the (9Z)-9-pentacosenoic acid displaying an IC50 = 54 μM and the 9-pentacosynoic acid not inhibiting the enzyme at all. Fatty acid chain length and position of the unsaturation was important for the observed inhibition. None of the synthesized fatty acids were toxic (IC50 > 500 μM) towards peripheral blood mononuclear cells. Molecular modeling studies indicated the structural determinants underlying the biological activity of the most potent compounds. These results provide new insights into the structural requirements that must be present in fatty acids so as to enhance their inhibitory potential towards HIV-RT.
- Moreira, Lizabeth Giménez,Orellano, Elsie A.,Rosado, Karolyna,Guido, Rafael V. C.,Andricopulo, Adriano D.,Soto, Gabriela Ortiz,Rodríguez, José W.,Sanabria-Ríos, David J.,Carballeira, Néstor M.
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p. 1043 - 1050
(2015/10/05)
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- Highly efficient preparation of selectively isotope cluster-labeled long chain fatty acids via two consecutive Csp3-Csp3 cross-coupling reactions
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An efficient synthesis involving two copper-catalyzed alkyl-alkyl coupling reactions has been designed to easily access doubly isotope-labeled fatty acids. Such NMR- and IR-active compounds were obtained in excellent overall yields and will be further used for determining the conformation of an alkyl chain of lipidic biomolecules upon interaction with proteins.
- Lethu, Sebastien,Matsuoka, Shigeru,Murata, Michio
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supporting information
p. 844 - 847
(2014/03/21)
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- First total synthesis of acetylenic alcohol 15-methyltricosa-2,4-diyne-1, 6-diol (strongylodiol-G) derived from marine sponge
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The first total and efficient synthesis of a naturally occurring acetylenic alcohol 15-methyltricosa-2,4-diyne-1,6-diol (strongylodiol-G) derived from marine sponge involving nine steps has been described. 1-Bromo-9- methyloctadecane (5) and hex-6-tetrahydropyranyloxyhex-2,4-diyn-1-al (9) which were initially synthesised separately starting from 1,8-octanediol (1) and propargyl alcohol (6), respectively, have been used as the final intermediates to obtain the title compound. The key steps in the synthesis involved ionic liquid-mediated bromination of 1,8-octanediol (1), tetrahydropyranylation of 8-bromooctan-1-ol (2) using acidic ionic liquid [bmim]HSO4 and monotetrahydropyranylation of hex-2,4-yn-1,6-diol (7) using ultrasonic energy.
- Gupta, Neeraj,Shallu,Kad, Goverdhan Lal,Singh, Jasvinder
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p. 424 - 430
(2014/04/17)
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- Long-chain triazolyl acids as inhibitors of osteoclastogenesis
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Saturated fatty acids (e.g., palmitic acid) are known to moderately inhibit the development of osteoclasts in vitro. In pursuit of more effective inhibitors of osteoclastogenesis we explored two new classes of palmitic acid analogues containing either an ether or triazolyl group at various positions along the chain. The compounds were evaluated for their ability to inhibit the formation of osteoclasts in primary mouse bone marrow cultures. The oxyacids were generally prepared by condensation of the appropriate alkyl halides and diols, followed by Jones oxidation. The triazolyl acids were prepared by copper-catalysed click chemistry between alkyl azides and acetylenic acids, or with the appropriately-protected azides and alkynes, followed by deprotection and oxidation. The oxyacids were little more effective than palmitic acid, but the triazolyl analogues were much more effective osteoclastogenesis inhibitors, especially when the triazole was distant from the acid unit.
- Marshall, Andrew J.,Lin, Jian-Ming,Grey, Andrew,Reid, Ian R.,Cornish, Jillian,Denny, William A.
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p. 4112 - 4119
(2013/07/27)
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- Simple and efficient method for tetrahydropyranylation of alcohols and phenols by using silica supported sodium hydrogen sulphate as a catalyst
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A Simple and efficient process for tetrahydropyranylation of alcohols and phenols has been developed by reacting with dihydropyran at room temperature in presence of catalytic amount of silica supported sodium hydrogen sulphate.
- Ravi Kumar,Satyanarayana,Srinivasa Reddy
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experimental part
p. 3876 - 3878
(2012/09/21)
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- Efficient synthesis of unsaturated 1-monoacyl glycerols for in meso crystallization of membrane proteins
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A highly efficient synthesis of unsaturated 1-monoacyl glycerols was established to fulfill the pressing need for materials that form lipidic mesophases utilized in membrane protein crystallization. Georg Thieme Verlag Stuttgart.
- Fu, Yu,Weng, Yue,Hong, Wen-Xu,Zhang, Qinghai
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experimental part
p. 809 - 812
(2011/06/21)
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- A biomimetic approach to the synthesis of a mycolic acid motif
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A new method for the stereoselective synthesis of the (R,R)-β-hydroxy-α-alkyl fatty acid fragment of mycolic acids, via an asymmetric anti-aldol reaction is reported. The 'mycolic acid motif' fragment was prepared in three steps and >98% ee.
- Driver, Cathryn H.S.,Balogun, Mohammed O.,Toschi, Gianna,Verschoor, Jan A.,Baird, Mark S.,Pilcher, Lynne A.
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supporting information; scheme or table
p. 1185 - 1186
(2010/04/23)
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- First syntheses of model long-chain trichloro[ω-(trimethylsilyl)alkynyl]silanes suitable for self-assembled monolayers on silicon surfaces
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The preparation of the title compounds involves the introduction of the required Me3SiC{triple bond, long}C and trichlorosilyl groups at the termini of the alkyl chain via derivatization of easily accessible and inexpensive materials/reagents. Trichloro[ω-(trimethylsilyl)alkynyl]silanes are useful for the linkage to a hydroxylated silicon surface for multilayer formation and for further chemical modification of the tail group of the monolayer.
- Banaszak, Estelle,Xu, Li-Wen,Bardeau, Jean-Fran?ois,Castanet, Anne-Sophie,Mortier, Jacques
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experimental part
p. 3961 - 3966
(2009/09/30)
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- 4-DIMETHYLAMINOBUTYRIC ACID DERIVATIVES
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This invention relates to novel 4-dimethylaminobutyric acid derivatives of the formula wherein A1, A2, R1, m and n are as defined in the description and in the claims, as well as pharmaceutically acceptable salts thereof. These compounds inhibit carnitine palmitoyl transferase (CPT) activity, in particular CPT2 activity, and can be used as medicaments in methods for the treatment of diseases modulated by CPT2 inhibitors.
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(2009/10/31)
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- Microwave and ultrasound assisted synthesis of 16-methyl-8(Z)-heptadecenoic and 16-methyl-6(Z)-heptadecenoic acids
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The first total synthesis of two novel iso-branched heptadecenoic acids, the major components in a species of bacterium, Micrococcus, has been carried out using a rapid, simple and clean process utilizing microwave and ultrasound radiations.
- Kaur, Jasamrit,Kaur, Irvinder,Sonu,Kad, Goverdhan L.,Singh, Jasvinder
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p. 155 - 158
(2008/09/20)
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- The first syntheses of single enantiomers of the major methoxymycolic acid of Mycobacterium tuberculosis
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The synthesis of three stereoisomers of a major homologue of the methoxymycolic acids present in Mycobacterium tuberculosis is described.
- Al Dulayymi, Juma'a R.,Baird, Mark S.,Roberts, Evan,Deysel, Madrey,Verschoor, Jan
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p. 2571 - 2592
(2007/10/03)
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- In vivo studies of dialkynoyl analogues of DOTAP demonstrate improved gene transfer efficiency of cationic liposomes in mouse lung
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A novel set of dialkynoyl analogues of the cationic, gene delivery lipid DOTAP (1) was synthesized. Structure-activity studies demonstrate that replacement of the cis-double bonds of DOTAP with triple bonds in varying positions alters both the physical properties of the resultant cationic liposome-DNA complexes and their biological functionalities, both in vitro and in vivo. Particularly, in vivo studies demonstrate that pDNA transfection of mouse lung endothelial cells with lead analogue DS(14-yne)TAP (4):cholesterol lipoplexes exhibits double the transfection level with less associated toxicity relative to the well-established DOTAP:cholesterol system. In fact, 4:cholesterol delivers up to 3 times the dose of pDNA in mice than can be tolerated by DOTAP, leading to nearly 3 times greater marker-gene expression. X-ray diffraction studies suggest that lipoplexes containing analogue 4 display increased stability at physiological temperatures. Our results thus suggest that analogue 4 is a potentially strong candidate for the gene therapy of lung tumors.
- Fletcher, Steven,Ahmad, Ayesha,Perouzel, Eric,Heron, Andrew,Miller, Andrew D.,Jorgensen, Michael R.
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p. 349 - 357
(2007/10/03)
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- A dialkynoyl analogue of DOPE improves gene transfer of lower-charged, cationic lipoplexes
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Positively-charged gene delivery agents, such as cationic liposomes, typically prepared by mixing a cationic lipid and a neutral lipid in a 1: 1 molar ratio, exhibit a fundamental flaw: on the one hand, the charge encourages cell uptake; on the other hand, the charge leads to aggregation in vivo with anionic serum components. We herein report a more phase-stable analogue of the zwitterionic and fusogenic lipid DOPE that allows for the reduction of the cationic lipid component of the liposome from 50 to 9 mol% with almost no apparent loss in transfection activity. This reduction in charge may induce important in vivo stability whilst still imparting high cell uptake and transgene expression. The Royal Society of Chemistry 2006.
- Fletcher, Steven,Ahmad, Ayesha,Perouzel, Eric,Jorgensen, Michael R.,Miller, Andrew D.
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p. 196 - 199
(2007/10/03)
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- Development of the first potential covalent inhibitors of anandamide cellular uptake
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On the basis of the chemical structures of two previously developed metabolically stable and relatively potent inhibitors of anandamide uptake, OMDM-1,2, two series of potential covalent inhibitors of anandamide cellular reuptake, which might be used for the molecular characterization of the protein(s) involved in the membrane transport of endocannabinoids, have been designed and synthesized. Most of the compounds inhibited uptake to a varied extent and in a generally enantio-sensitive manner when co-incubated with [ 14C]anandamide, but only three of them, the photoactivatable 1a (OMDM-37), 1b (OMDM-39), and 8 (Lo395), also produced a significant inhibition of uptake following the preincubation only of the cells, and this effect was significantly enhanced following UV exposure only in the case of 8. None of the new compounds inhibited [14C]anandamide hydrolysis with IC 50 50 μM, except for 1b.
- Moriello, Aniello Schiano,Balas, Laurence,Ligresti, Alessia,Cascio, Maria Grazia,Durand, Thierry,Morera, Enrico,Ortar, Giorgio,Di Marzo, Vincenzo
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p. 2320 - 2332
(2007/10/03)
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- Synthesis and characterization of 3,13- and 2,13-octadecadienyl compounds for identification of the sex pheromone secreted by a clearwing moth, Nokona pernix
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Several geometrical isomers of 3,13- and 2,13-octadecadien-1-ols and their acetates were synthesized starting from 1,8-octanediol or 1,9-nonanediol utilizing acetylene coupling reactions. In addition to commercially available compounds, all geometrical isomers of each dienyl compound were analyzed by NMR and GC-MS to accumulate chemical data for studies of sex pheromones secreted from clearwing moths classified into the family Sesiidae of Lepidoptera. Although acetoxy derivatives of the 3,13- and 2,13-dienes showed almost the same mass spectra, the alcohols were distinguished by comparing the relative intensities of [M - 18]+ at m/z 248, indicating direct differentiation of the two positional isomers without derivatization. Furthermore, each geometrical isomer eluted from a high-polar GC column with a different retention time. Base on these data, a pheromone gland extract of a sesiid moth, Nokona pernix, was analyzed by GC-EAD and GC-MS, and two EAG-active components were identified, viz., the (3E,13Z)- and (3Z,13Z)-isomers of 3,13-octadecadien-1-ol in a ratio of 9:1. In the field, the synthetic compounds mixed in 9:1 ratio attracted N. pernix males well, while a single component scarcely attracted the males. The number of attracted males peaked in the middle of June, and a small second peak was observed in August.
- Naka, Hideshi,Nakazawa, Tomotake,Sugie, Mieko,Yamamoto, Masanobu,Horie, Yoshiteru,Wakasugi, Ryohei,Arita, Yutaka,Sugie, Hajime,Tsuchida, Koji,Ando, Tetsu
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p. 508 - 516
(2008/02/10)
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- Ethynylation of the ether derivatives of ω-haloalkanols with lithium acetylide-ethylenediamide complex
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A new operationally simple and highly efficient procedure for the ethynylation of ether derivatives of ω-haloalkanols with lithium acetylide-ethylenediamine complex in N,N-dimethylacetamide is described.
- Karpinska,Lewandowska,Grodner
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p. 937 - 942
(2007/10/03)
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- Estrogen-linked platinum (II) complexes as anticancer agents
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wherein n may be 1, 2, 3, 4 or 5 when X is O, wherein n may be 2/3, 1, 4/3, 5/3, 2, 7/3, 8/3, 3, or 10/3 when X is C, wherein o may be 1, 2 or 3, wherein Y may be O or 17β-OH, wherein R1 may be selected from the group consisting of H, a straight alkyl group of 1 to 5 carbon atoms, a branched alkyl group of 3 to 5 carbon atoms, wherein R2 may be selected for the group consisting of H, a straight alkyl group of 1 to 4 carbon atoms, a branched alkyl group of 3 or 4 carbon atoms, F, Cl, Br, I, —CF3, —NO2, —OR1, —COR1 and —CH2OH. These compounds possess anticancer activity against hormono-dependent breast, uterus as well as ovarian cancer.
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(2008/06/13)
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- Sequential substitution of 1,2-dichloro-ethene: A convenient stereoselective route to (9Z,11E)-, (10E,12Z)- and (10Z,12Z)-[1-14C] conjugated linoleic acid isomers
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Conjugated linoleic acid (CLA) isomers are present in human foods derived from milk or ruminant meat. To study their metabolism, (9Z,11E)-, (10E,12Z)- and (10Z,12Z)-[1-14C]-octadecadienoic acids with high radiochemical and isomeric purities (> 98%) were prepared by stereoselective multi-step syntheses involving sequential substitution of 1,2-dichloro-ethene. In the case of the (9Z,11E) isomer, a first metal-catalyzed cross-coupling reaction between (E)-1,2-dichloro-ethene and 2-non-8-ynyloxy-tetrahydro-pyran, obtained from 7-bromo-heptan-1-ol, gave a conjugated chloroenyne. A second coupling reaction with hexylmagnesium bromide provided a heptadecenynyl derivative. Stereoselective reduction of the triple bond and bromination afforded (7E,9Z)-17-bromo-heptadeca-7,9-diene. Formation of the Grignard reagent and carbonation with 14CO2 gave (9Z,11E)-[1-14C]-octadeca-9,11-dienoic acid (overall yield from 7-bromo-heptan-1-ol, 14.4%). (10E,12Z)- and (10Z,12Z)-[1-14C]-octadeca-10,12-dienoic acids were synthesized by the same methodology using 1-heptyne, 8-bromo-octan-1-ol and, respectively, (E)-1,2-dichloro-ethene and its (Z) isomer (overall yield from 8-bromo-octan-1-ol, 13.1% (10E,12Z); 17.2% (10Z,12Z)). Impurities ( 2% if present) were identified as being (E,E) CLA isomers and were removed by RP-HPLC. Metabolism studies in animal are in progress.
- Loreau,Maret,Chardigny,Sebedio,Noel
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- Biosynthesis of epilachnene, a macrocyclic defensive alkaloid of the Mexican bean beetle
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The carbon skeleton of the azamacrolide epilachnene, the principal defensive alkaloid of Epilachna varivestis pupae, can be derived from oleic acid and serine. Analytical evidence from three experiments in which insects were fed (2H35)octadecanoic acid, (Z)-9- [11,11,12,12,13,13,14,14,15,15,16,16,17,17,18,18,18-2H17]octadecenoic acid and (Z)-9-[11,11,12,12,13,13,14,14,16,16,17,17,18,18,18-2H15]octadecenoic acid, indicates that only the C-15 methylene group of oleic acid is involved in the mechanism leading to carbon-nitrogen bond formation in epilachnene. Support for this scheme is provided by the observation of an unusual ion at m/z 170 in the electron-ionization mass spectrum of epilachnene, rationalized as CH2=CH-COO-CH2-CH2-NH+=CH-CH2-CH2-CH3.
- Attygalle, Athula B.,Svatos, Ales,Veith, Martin,Farmer, Jay J.,Meinwald, Jerrold,Smedley, Scott,Gonzalez, Andres,Eisner, Thomas
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p. 955 - 966
(2007/10/03)
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- Functionalized aliphatic P2/P2' analogs of HIV-1 protease inhibitor DMP323
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A series of analogs of HIV protease inhibitor DMP323 containing functionalized aliphatic P2/P2' groups was prepared and evaluated for HIV protease inhibition and antiviral activity in a cell-based assay. Asymmetric compounds with a 5-hydroxypentyl substituent at P2 and a benzylic substituent at P2' showed increased potency over the corresponding symmetrically substituted analogs.
- Smallheer, Joanne M.,McHugh, Robert J.,Chang, Chong-Hwan,Kaltenbach III, Robert F.,Worley, Tabitha V.,Klabe, Ronald M.,Bacheler, Lee T.,Rayner, Marlene M.,Erickson-Viitanen, Susan,Seitz, Steven P.
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p. 1365 - 1370
(2007/10/03)
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- Homologous long-chain alkanediols from Papaver leaf cuticular waxes
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In cuticular waxes from leaves of Papaver alpinum sensu Markgr., P. dubium L., P. nudicaule L., P. orientale L., P. rhoeas L. and P. somniferum L., six new alkanediols carrying one primary and one secondary hydroxyl function were identified. Five of them, docosane-1,3-diol, hexacosane-1,7- diol, octacosane-1,9-diol, nonacosane-1,10-diol and triacontane-1,11-diol, form a homologous series. Their molecular geometries and relative proportions suggest a biosynthetic relationship to the corresponding primary alkanols.
- Jetter, Reinhard,Riederer, Markus,Seyer, Andre,Mioskowski, Charles
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p. 1617 - 1620
(2007/10/03)
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- Pheromones of insects and their analogs. LII. Sythesis of dodec-9-en-1-yl and tetradec-11-en-1-yl acetates from the products of the partial ozonolysis of cycloocta-1z,5z-diene and cyclodeca-1e,5z-diene
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A new approach to the synthesis of octane-1,8-and decane-1,10-diols based on the partial ozonolysis of cyclic oligomers has been developed.
- Odinokov,Botsman,Gladysheva
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p. 381 - 383
(2007/10/03)
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- Useful Direct Conversion of Tetrahydropyranyl Ethers of Fatty Alcohols into Fatty Acids
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Tetrahydro-2-pyranyl ethers from fatty primary alcohols can be converted in a one-step procedure into the corresponding carboxylic acids in high yields.This process avoids the synthesis of symmetrical esters, particularly for long-chain compounds.This reaction proved to be useful, for instance, to produce polyunsaturated fatty acids immediately before their biological testing. - Key words: Oxidation; polyunsaturated fatty acids; tetrahydropyranyl ethers
- Gruiec, Regine,Noiret, Nicolas,Patin, Henri
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p. 1083 - 1085
(2007/10/03)
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- Tetrazole-substituted urea acat inhibitors
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Novel ACAT inhibitors useful in the treatment of atherosclerosis which are tetrazole-substituted ureas,
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- Studies related to fatty acids desaturation. II. Preparation of iso-linoleic and iso-vernolic acids
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New iso-vernolic and iso-linoleic acids have been prepared in order to study their potential inhibition action during in vivo desaturation of oleic acid in vegetal sources. - Keywords: Δ12-desaturase / modified fatty acids / Z,ω-octenyl bromides / iso-linoleic acids / iso-vernolic acids
- Gruiec, Regine,Noiret, Nicolas,Patin, Henri
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p. 699 - 705
(2007/10/02)
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- Total Synthesis of (2S,3S,4R)-2--16-methylheptadecane-1,3,4-triol 3,4-dibenzoate, a Partially Protected Ceramide Part of Sponge Cerebrosides
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(2S,3S,4R)-2--16-methylheptadecane-1,3,4-triol 3,4-dibenzoate 32, apertially protected ceramide part of a cerebroside from the marine sponge Halichondria japonica, has been synthesized from L-ascorbic acid, and its absolute stereochemistry has been determined.The key steps in the synthesis include the regioselective ring opening of chiral epoxide 5 with a 2-alkyl-2-lithio-1,3-dithiane and the introduction of a hydroxymethylene synthon using Dondoni's protocol to assemble C(1) and C(2) functionality.
- Nakashima, Hideki,Hirata, Norihiko,Iwamura, Takeru,Yamagiwa, Yoshiro,Kamikawa, Tadao
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p. 2849 - 2858
(2007/10/02)
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- Synthesis of Alkylphenols and -catechols from Plectranthus albidus (Labiatae)
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In the preceding paper, we described the isolation and structure elucidation of a series of even-numbered phenol- or pyrocatechol-derived 1-arylalkane-5-ones.To establish the assigned structures unambiguously and to have larger quantities available for physiological testing, the following compounds were prepared: in the alkylphenol series, 1-(4'-hydroxyphenyl)tetradecan-5-one (2a), 1-(4'-hydroxyphenyl)hexadecan-5-one (2b), and 1-(4'-hydroxyphenyl)octadecan-5-one (2c); in the alkylcatechol series, 1-(3',4'-dihydroxyphenyl)decan-5-one (3a; not isolated as a natural compound), 1-(3',4'-dihydroxyphenyl)dodecan-5-one (3b), 1-(3',4'-dihydroxyphenyl)tetradecan-5-one (3c), 1-(3',4'-dihydroxyphenyl)hexadecan-5-one (3d), 1-(3',4'-dihydroxyphenyl)octadecan-5-one (3e), and 1-(3',4'-dihydroxyphenyl)icosan-5-one (3f); in the alkenylphenol series, (Z)-1-(4'-hydroxyphenyl)octadec-13-en-5-one (4a) and (E)-1-(4'-hydroxyphenyl)octadec-13-en-5-one (4b); in the alkenylcatechol series, (E,E)-1-(3',4'-dihydroxyphenyl)deca-1,3-dien-5-one (1) and (Z)-1-(3',4'-dihydroxyphenyl)octadec-13-en-5-one (5).All compounds proved to be identical with the previously assigned structures.Compound 1 was synthesized by regioselective aldol condensation of heptan-2-one with (E)-3-(3',4'-dimethoxyphenyl)prop-2-enal (6d; Scheme 1), the phenols 2a-c and the catechols 3a-f by addition of the corresponding alkyl Grignard reagent to 5-(4'-methoxyphenyl)- or 5-(3',4'-dimethoxyphenyl)pentanal (17c and 18c, resp.; Scheme 4), and the olefins 4a, 4b and 5 from 17c or 18c via the 9-O-silyl-protected 13-(4'-methoxyphenyl)- or 13-(3',4'-dimethoxyphenyl)tridecanals (26 and 27, resp.) and Wittig olefination as the key steps (Scheme 5).
- Buergi, Christoph,Liu, Gui,Rueedi, Peter
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p. 1901 - 1915
(2007/10/02)
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- SYNTHESIS OF DODEC-10E-EN-1-YL ACETATE - THE SEX PHEROMONE OF Lithocolletis blancardella
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Dodec-10E-en-1-yl acetate - the sex pheromone of the apple leaf miner moth - has been obtained by a four-stage synthesis from monomethyl azelate and crotyl acetate.Its IR, PMR, and mass spectra are given.
- Plugar', N. Ya.,Verba, G. G.,Abduvakhabov, A. A.,Kamaev, F. G.
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p. 455 - 457
(2007/10/02)
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- Design, synthesis, and activity of membrane-disrupting bolaphiles
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Four new classes of bolaphiles ("double-headed" single-chain surfactants) have been prepared, via condensation of an homologous series of linear saturated, olefinic, and acetylenic α,ω-dicarboxylic acids with hexaethylene glycol, and evaluated for their ability to induce the release of 5(6)-carboxyfluorescein (CF) entrapped within large unilamellar vesicles derived from 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC). Operationally, the membrane-disrupting activity of the bolaphiles has been found to vary by a factor of ca. 100, when the total number of carbon atoms which separate the carboxylate moieties range from 12 to 24; the most active bolaphile is approximately three times more active than Triton X-100. When the affinity of the bolaphiles toward POPC membranes is considered, the intrinsic membrane-disrupting activity varies by a factor of ca. 230. A "loop" model is proposed to account for the general trends in bolaphile activity that are observed, where the depth of loop penetration and loop width are presumed to be the key factors involved in determining membrane-disrupting activity. The potential utility of these surfactants as antimicrobial agents, and as anti-HIV agents in particular, is briefly discussed.
- Jayasuriya, Nimal,Bosak, Stanislav,Regen, Steven L.
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p. 5844 - 5850
(2007/10/02)
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- INSECT PHEROMONES AND THEIR ANALOGUES. XVI. PRACTICAL SYNTHESIS OF HEXADEC-9Z-ENAL - A COMPONENT OF THE SEX PHEROMONE OF THE COTTON BOLLWORM Heliothis armigera
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A synthesis of hexadec-9Z-enal - a component of the sex pheromone of the cotton bollworm Heliothis armigera (Huebner) - based on cyclooctene (I) is proposed.Through a solution of 22 g of (I), 250 ml of cyclohexane, and 40 ml of MeOH is passed (at 5 deg C) 0.2 M O3/O2, the solution is decanted off, and the precipitated ozonide is dissolved in 200 ml of MeOH and is reduced with 19 g of NaBH4 (40 deg C) with the isolation, after the usual working up, of 23.4 g of octane-1,8-diol (II).From 0.5 mole of (II) and 0.6 mole of 45percent HBr 8-bromooctan-1-ol (III) is obtained and this is converted into 1-(2-(THPL)oxy)-8-bromooctane (IV).The condensation of (IV) with oct-1-yne (Ar, LiNH2, HMPTA, 10 deg C, 1 h, and then 55 deg C, 10 h) leads to 1-(2-THPL-oxy)hexadec-9-yne (V) the hydrolysis of which (MeOH, H2O, p-TsOH, 20 deg C for 20 h) yields hexadec-9-yn-ol (VI).The reduction of (VI) (Et2O, iso-BuMgBr, Cp2TiCl2, 0 deg C, 15 min, then 20 deg C, 1 h) yields hexadec-9Z-en-1-ol (VII).The oxidation of (VII) (PyHCrO3+ Cl-, CH2Cl2, 20 deg C, 2 h) gives hexadec-9Z-enal (VIII).Characteristics of the compounds (yield (percent), nD20(25): (II) - 80, mp 61-62 deg C; (III) - 75, 1.4807; (IV) - 99, -; (V) - 52, 1,4650; (VI) - 85, 1.4657; (VII) - 99, 1.4650; (VIII) - 98, 1.4600.Characteristics of the IR and PMR spectra of compounds (V-VII) are given.
- Odinolov, V. N.,Dzhemilev, U. M.,Ishmuratov, G. Yu.,Botsman, L. P.,Vostrikova, O. S.,et al.
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p. 242 - 244
(2007/10/02)
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- SYNTHESIS AND BIOMETHYLENATION OF TWO HOMOALLYLICALLY FLUORINATED OLEIC ACIDS
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Methyl 7-fluorooleate and methyl 12-fluorooleate have been synthesized in racemic form.Both of these compounds are incorporated into L. plantarum but are methylenated to a different extent.
- Buist, Peter H.,Findlay, Judy M.,Leger, Gabriel,Pon, Robert A.
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p. 3891 - 3894
(2007/10/02)
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- PHOTOLACTONIZATION : A NOVEL SYNTHETIC ENTRY TO MACROLIDES
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o-Quinol acetates, hydroxyalkyalted at C(6), are easily accesible from simple phenols by Wessely acetoxylation (preferentially catalyzed by BF3).On UV irradiation ( in the presence of an appropriate tertiary amine), they are smoothly converted to macrocyclic lactones.Subtle conditions have been elaborated to lead to high overall yields, and the scope of the conversion of phenols to macrolides has been elucidated.
- Quinkert, Gerhard,Billhardt, Uta-Maria,Jakob, Harald,Fischer, Gerd,Glenneberg, Juergen,et al.
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p. 822 - 861
(2007/10/02)
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- Directed Synthesis of Translationally Isomeric -Catenanes
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In a multi-step reaction sequence the tetrahydroxymetacyclophane 12c is synthesized.Acetalisation with 1,25-dichloro-13-pentacosanone followed by nitration and reduction afforded the diamine 13c.By cyclization of this compound in 2-pentanol with sodium carbonate and sodium iodide under high dilution conditions the monomeric products 16, 17, and 18 are obtained in yields of 21.4, 7.7, and 0,9percent, respectively.On the basis of mass, 13C NMR and 1H NMR spectra the structure of these compounds is discussed.Starting from the precatenane 16 the -catenanes 25a,b,c and 26a,b,c are obtained in a multi-step reaction sequence.The structure of these compounds is confirmed by mass, 13C NMR, and 1H NMR spectroscopic investigations.
- Rissler, Klaus,Schill, Gottfried,Fritz, Hans,Vetter, Walter
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p. 1374 - 1399
(2007/10/02)
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- SYNTHESIS OF THE RACEMIC FORM OF (Z)-1,17-DIAMINOOCTADEC-9-ENE, AN ALIPHATIC DIAMINE FROM COCCINELLIDAE. DETERMINATION OF THE ABSOLUTE CONFIGURATION OF THE (+)-NATURALLY-OCCURRING ANTIPODE
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The total synthesis of the title compound (1) has been achieved.Also reported is the use of lanthanide induced shifts in 1H NMR spectroscopy to assign the absolute configuration of the α-carbon atom in chiral primary α-methylalkylamines.Application of this empirical method to natural (+)-1 shows that it has the R-configuration at C-17.
- Braconnier, M.F.,Braekman, J.C.,Daloze, D.
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p. 605 - 614
(2007/10/02)
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- INSECT PHEROMONES AND THEIR ANALOGUES. IX. STEREOSPECIFIC SYNTHESIS OF (Z)-DODECA-9,11-DIENYL ACETATE, A COMPONENT OF THE SEX PHEROMONE OF THE COTTON BOLLWORM MOTH Diparopsis cactanea
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A method has been developed for the stereospecific synthesis of (Z)-dodeca-9,11-dienyl acetate, a component, together with the corresponding (E) isomer, of the sex pheromone of the red cotton bollworm moth, that is based on the coupling of vinylacetylene with either 8-hydroxyoctanal or 8-bromoctan-1-ol to form a C12 enynic compound in which the acetylenic bond is then reduced stereospecifically with 9-borabicyclononane.
- Balezina, G. G.,Ishmuratov, G. Yu.,Odinokov, V. N.,Selimov, F. A.,Dzhemilev, U. M.,Tolstikov, G. A.
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p. 354 - 357
(2007/10/02)
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- Stereoselective Syntheses of E- and Z-9,11-Dodecadien-1-yl Acetates: The Major Sex Pheromones of the Red Bollworm Moth
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The sex pheromones 1 and 2 of the red bollworm moth were synthesized in a highly stereoselective manner.The key step of their syntheses was the olefination reaction of E- and Z-allyl phenyl sulfones 8 and 12, affording the corresponding dienes 9 and 15, respectively.Keywords - E-9,11-dodecadien-1-yl acetate; Z-9,11-dodecadien-1-yl acetate; sex pheromone; red bollworm moth; allyl sulfone; tri-n-butylstannylmethyl iodide
- Ochiai, Masahito,Ukita, Tatsuzo,Fujita, Eiichi
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p. 1641 - 1645
(2007/10/02)
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- A STEREOSPECIFIC SYNTHESIS OF 12-ACETOXY-1,3-DODECADIENE, THE SEX PHEROMONE OF DIPAROPSIS CASTANEA (HAMPSON)
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A stereospecific synthesis of 12-acetoxy-1,3(E)-dodecadiene, 1, the pheromone of the Diparopsis castanea Hampson, via the alkylation of the anion of 2-(2-propyne-1-oxy)tetrahydropyran, 5a, and successive reduction with LiAlH4, is described.
- Cardillo, Giuliana,Orena, Mario,Porzi, Gianni,Sandri, Sergio
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p. 523 - 526
(2007/10/02)
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- SYNTHESIS OF HIGHER ACETYLENIC ALCOHOLS
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The alkylation of 1-alkynes in various solvents was investigated, and the optimum conditions for the production of acetylenic alcohols were obtained.
- Kovalev, B. G.,Matveeva, E. D.,Stan, V. V.,Vovk, G. A.,Yudin, L. G.,Kost, A. N.
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p. 1728 - 1733
(2007/10/02)
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- INSECT SEX PHEROMONES. STEREOSELECTIVE SYNTHESIS OF SEVERAL (Z)- AND (E)-ALKEN-1-OLS, THEIR ACETATES, AND OF (9Z,12E)-9,12-TETRADECADIEN-1-YL ACETATE
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Several female sex pheromone components produced by moths belonging to the order of Lepidoptera, and potential attractants of Dacus oleae (Diptera:Tripetidae) have been synthesized in high chemical and stereoisomeric purity by improved acetylenic routes involving alkylation of lithium 1-alkyn-1-ides in HMPT, followed by (Z) and (E) highly stereoselective reduction of the derived internal alkynes.Particular care has been paid to optimize the parameters of the reactions used and to evaluate the chemical and isomeric purity of the reaction products.The compounds synthesized include (Z)- and (E)-5-nonen-1-ol, (Z)- and (E)-7-dodecen-1-yl acetate, (Z)- and (E)-7-teradecen-1-yl acetate, (Z)- and (E)-7-nonen-1-ol, (Z)- and (E)-9-tetradecen-1-yl acetate, (Z)- and (E)-10-tetradecen-1-yl acetate, (Z)- and (E)-11-tetradecen-1-yl acetate.Pure (Z)-6-nonen-1-ol, which is an attractant of olive fruit fly, D. oleae, and very probably, a constituent of the sex pheromone of females of this insect, has been prepared by a rather efficient copper-catalyzed reaction between (Z)-3-hexen-1-ylmagnesium bromide and oxetane. (9Z,12E)-9,12-Tetradecadien-1-yl acetate, which is the pheromone of Anagasta kuenniella, Ephestia elutella, Cadra figulella, Spodoptera exigua, S. litura, and a component of the sex pheromones of several other Lepidoptera, has been conveniently prepared by using the copper-catalyzed coupling reaction between (E)-1-chloro-2-butene and 10-tetrahydropyranyloxy-1-decenylmagnesium bromide, followed by acetylation and Z-stereoselective reduction of the derived 1,4-enyne.All syntheses have been conducted on a scale to yield less than 50 mmol of the pure sex pheromone components, but seem adaptable for much larger quantities.
- Rossi, Renzo,Carpita, Adriano,Gaudenzi, Loretta,Quirici, Maria Grazia
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p. 237 - 246
(2007/10/02)
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