- A Systematic Study of Unsaturation in Lipid Nanoparticles Leads to Improved mRNA Transfection In Vivo
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Lipid nanoparticles (LNPs) represent the leading concept for mRNA delivery. Unsaturated lipids play important roles in nature with potential for mRNA therapeutics, but are difficult to access through chemical synthesis. To systematically study the role of unsaturation, modular reactions were utilized to access a library of 91 amino lipids, enabled by the synthesis of unsaturated thiols. An ionizable lipid series (4A3) emerged from in vitro and in vivo screening, where the 4A3 core with a citronellol-based (Cit) periphery emerged as best. We studied the interaction between LNPs and a model endosomal membrane where 4A3-Cit demonstrated superior lipid fusion over saturated lipids, suggesting its unsaturated tail promotes endosomal escape. Furthermore, 4A3-Cit significantly improved mRNA delivery efficacy in vivo through Selective ORgan Targeting (SORT), resulting in 18-fold increased protein expression over parent LNPs. These findings provide insight into how lipid unsaturation promotes mRNA delivery and demonstrate how lipid mixing can enhance efficacy.
- Lee, Sang M.,Cheng, Qiang,Yu, Xueliang,Liu, Shuai,Johnson, Lindsay T.,Siegwart, Daniel J.
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supporting information
p. 5848 - 5853
(2021/02/05)
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- A facile and versatile electro-reductive system for hydrodefunctionalization under ambient conditions
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A general electrochemical system for reductive hydrodefunctionalization is described, employing the inexpensive and easily available triethylamine (Et3N) as a sacrificial reductant. This protocol is characterized by facile operation, sustainable conditions, and exceptionally wide substrate scope covering the cleavage of C-halogen, N-S, N-C, O-S, O-C, C-C and C-N bonds. Notably, the selectivity and capability of reduction can be conveniently switched by simple incorporation or removal of an alcohol as a co-solvent.
- Huang, Binbin,Guo, Lin,Xia, Wujiong
-
supporting information
p. 2095 - 2103
(2021/03/26)
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- Nickel-Catalyzed Inter- and Intramolecular Aryl Thioether Metathesis by Reversible Arylation
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A nickel-catalyzed aryl thioether metathesis has been developed to access high-value thioethers. 1,2-Bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional-group-tolerant reaction. Furthermore, synthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis that does not involve alkene bonds. In-depth organometallic studies support a reversible Ni0/NiII pathway to product formation. Overall, this work not only provides a more sustainable alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information that are highly relevant to the further development and application of unusual single-bond metathesis reactions.
- Delcaillau, Tristan,Bismuto, Alessandro,Lian, Zhong,Morandi, Bill
-
supporting information
p. 2110 - 2114
(2019/12/24)
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- 1,2,3-Triazole tethered 1,2,4-trioxanes: Studies on their synthesis and effect on osteopontin expression in MDA-MB-435 breast cancer cells
-
Artemisinin and its analogs have shown potent anticancer activity in primary cancer cultures and cell lines by inhibiting cancer proliferation, metastasis, and angiogenesis. Despite its apparent compatibility to normal cells and low IC50 values
- Pasupuleti, Bala Gangadhar,Khongsti, Kitboklang,Das, Bidyadhar,Bez, Ghanashyam
-
-
- Manganese-Catalyzed Stereospecific Hydroxymethylation of Alkyl Tosylates
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The development of a stereospecific hydroxymethylation of alkyl tosylates using an inexpensive, first-row catalyst is described. The transformation proceeds under mild conditions with low pressure to deliver homologated alcohols as products. Chiral, nonracemic β-branched primary alcohols are obtained with high enantiospecificity from easily accessed secondary alkyl substrates. Simple modification of the reaction system also permits access to α-d2 alcohols. These studies use anionic metal carbonyl catalysis to access a synthetic equivalent of the challenging hydroxymethyl anion from carbon monoxide.
- Shenouda, Hannah,Alexanian, Erik J.
-
supporting information
p. 9268 - 9271
(2019/11/19)
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- Iron-Catalyzed Hydroamination and Hydroetherification of Unactivated Alkenes
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The hydrofunctionalization of alkenes, explored for over 100 years, offers the potential for a direct, atom-economical approach to value-added products. While thermodynamically favored, the kinetic barrier to such processes necessitates the use of catalysts to control selectivity and reactivity. Modern variants typically rely on noble metals that require different ligands for each class of hydrofunctionalization, thereby limiting generality. This Letter describes a general iron-based system that catalyzes the hydroamination and hydroetherification of simple unactivated olefins.
- Marcyk, Paul T.,Cook, Silas P.
-
supporting information
p. 1547 - 1550
(2019/03/08)
-
- Synthesis and biological evaluation of chemical tools for the study of Dolichol Linked Oligosaccharide Diphosphatase (DLODP)
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Citronellyl- and solanesyl-based dolichol linked oligosaccharide (DLO) analogs were synthesized and tested along with undecaprenyl compounds for their ability to inhibit the release of [3H]OSP from [3H]DLO by mammalian liver DLO diphosphatase activity. Solanesyl (C45) and undecaprenyl (C55) compounds were 50–500 fold more potent than their citronellyl (C10)-based counterparts, indicating that the alkyl chain length is important for activity. The relative potency of the compounds within the citronellyl series was different to that of the solanesyl series with citronellyl diphosphate being 2 and 3 fold more potent than citronellyl-PP-GlcNAc2and citronellyl-PP-GlcNAc, respectively; whereas solanesyl-PP-GlcNAc and solanesyl-PP-GlcNAc2were 4 and 8 fold more potent, respectively, than solanesyl diphosphate. Undecaprenyl-PP-GlcNAc and bacterial Lipid II were 8 fold more potent than undecaprenyl diphosphate at inhibiting the DLODP assay. Therefore, at least for the more hydrophobic compounds, diphosphodiesters are more potent inhibitors of the DLODP assay than diphosphomonoesters. These results suggest that DLO rather than dolichyl diphosphate might be a preferred substrate for the DLODP activity.
- Bosco, Micha?l,Massarweh, Ahmad,Iatmanen-Harbi, Soria,Bouhss, Ahmed,Chantret, Isabelle,Busca, Patricia,Moore, Stuart E.H.,Gravier-Pelletier, Christine
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p. 952 - 964
(2016/10/25)
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- Structure-Odor Activity Studies on Monoterpenoid Mercaptans Synthesized by Changing the Structural Motifs of the Key Food Odorant 1-p-Menthene-8-thiol
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1-p-Menthene-8-thiol (1) has been discovered as the key odorant in grapefruit juice several decades ago and contributes to the overall odor of the fruit with an extremely low odor threshold of 0.000034 ng/L in air. This value is among the lowest odor thresholds ever reported for a food odorant. To check whether modifications in the structure of 1 would lead to changes in odor threshold and odor quality, 34 mercapto-containing p-menthane and 1-p-menthene derivatives as well as several aromatic and open-chain mercapto monoterpenoids were synthesized. Eighteen of them are reported for the first time in the literature, and their odor thresholds and odor qualities as well as analytical data are supplied. A comparison of the sensory data with those of 1 showed that hydrogenation of the double bond led to a clear increase in the odor threshold. Furthermore, moving the mercapto group into the ring always resulted in higher odor thresholds compared to thiols with a mercapto group in the side chains. Although all tertiary thiols always exhibited low odor thresholds, none of the 31 compounds reached the extremely low threshold of 1. Also, none of the synthesized mercapto monoterpenoids showed a similar odor quality resembling grapefruit. Although the saturated and aromatic analogues exhibited similar scents as 1, the aromas of the majority of the other compounds were described as sulfury, rubber-like, burned, soapy, or even mushroom-like. NMR and MS data as well as retention indices of the 23 newly reported sulfur-containing compounds might aid in future research to identify terpene-derived mercaptans possibly present in trace levels in foods.
- Schoenauer, Sebastian,Schieberle, Peter
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p. 3849 - 3861
(2016/06/01)
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- Pheromone synthesis. Part 259: Synthesis of seven methyl-branched hydrocarbons as the pheromone candidates for female Korean apricot wasp, Eurytoma maslovskii
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Seven new methyl-branched hydrocarbons were synthesized, which were the pheromone candidates of the female Korean apricot wasp (Eurytoma maslovskii). They are (Z)-15-methyl-7-nonacosene (1), (Z)-17-methyl-7-hentriacontene (2), 3,7-dimethylheptacosane (3), 8,12-dimethyltriacontane (4), 8,18-dimethyltriacontane (5), 3,7,11-trimethylnonacosane (6), and 3,7,17-trimethylnonacosane (7). All of them were synthesized as stereoisomeric mixtures, employing short and simple routes. Hydrocarbon 7 was synthesized via 4,8-dimethyldecanal (71, tribolure), the red flour beetle pheromone. The hydrocarbons 1,2,3 and 6 were identified by GC–MS analysis as the components (with unknown stereochemistry) of the female-specific secretion of E. maslovskii.
- Mori, Kenji,Yang, Chang Yeol
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p. 4593 - 4607
(2016/07/07)
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- Pheromone synthesis. Part 256: Synthesis of the four stereoisomers of 5,11-dimethylpentacosane, a new sex pheromone component of the male Galleria mellonella (L.), with high stereochemical purities as determined by the derivatization-HPLC analysis of the eight stereoisomers of 5,11-dimethyl-8-pentacosanol
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Abstract All the four stereoisomers of 5,11-dimethylpentacosane (>96.8% purity) were synthesized via the stereoisomers of 5,11-dimethyl-8-pentacosanol, whose stereoisomeric compositions could be determined precisely by their low temperature HPLC analysis after derivatization. 5,11-Dimethyl-8-pentacosanol was prepared by a Grignard reaction between 3-methylheptylmagnesium bromide and 4-methyloctadecanal, both of which were prepared from the commercially available enantiomers of citronellal (97-98% ee). Alternatively, (R)-3-methyl-1-heptanol could be prepared from methyl (R)-3-hydroxybutanoate (100% ee). Pd/C-catalyzed hydrogenation of a 5-methyl-1-alkene caused partial racemaization at C-5.
- Mori, Kenji,Akasaka, Kazuaki
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p. 4102 - 4115
(2015/06/02)
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- PRODUCTION METHOD OF 4,8-DIMETHYLDECANAL
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PROBLEM TO BE SOLVED: To provide a method of producing a mixture of (4R,8S)-4,8-dimethyldecanal and (4R,8R)-4,8-dimethyldecanal effective as pheromones for rust-red flour beetles and confused flour beetles, practically in a high yield through a small number of steps. SOLUTION: A method of producing a mixture of (4R,8S)-4,8-dimethyldecanal and (4R,8R)-4,8-dimethyldecanal includes a first step of tosylating (S)-citronellol to obtain a tosylate, a second step of reacting the tosylate with a Grignard reagent to obtain an alkene, a third step of epoxidating the alkene to obtain an epoxide, and a fourth step of cleaving the epoxide with a periodic acid to obtain 4,8-dimethyldecanal. COPYRIGHT: (C)2015,JPOandINPIT
- -
-
Paragraph 0009; 0012; 0018
(2016/12/12)
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- A dicationic, podand-like, ionic liquid water system accelerated copper-catalyzed azide-alkyne click reaction
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In this work, an effective, task specific, dicationic, podand-like ionic liquid was synthesized and applied to improve the capability features of click reaction. Moreover, to broaden the scope and decreasing the serious limitations of preparation methods of organic azides, a simple green procedure for the preparation of alkyl azides, the fundamental starting materials in click reactions, from alcohols under solvent-free conditions and microwave irradiation has been reported, for the first time.
- Javaherian, Mohammad,Kazemi, Foad,Ghaemi, Masoumeh
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p. 1643 - 1647
(2015/01/09)
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- Synthesis of all the stereoisomers of 6-methyl-2-octadecanone, 14-methyl-2-octadecanone, and 6,14-dimethyl-2-octadecanone, sex pheromone components of the Lyclene dharma dharma moth, from the enantiomers of citronellal
-
The enantiomers of citronellal were converted to all the stereoisomers of 6-methyl-2-octadecanone, 14-methyl-2-octadecanone, and 6,14-dimethyl-2- octadecanone, the female-produced sex pheromone components of the Lyclene dharma dharma moth. Three wellestablished procedures, the Wittig reaction, alkylation of alkynes, and acetoacetic ester synthesis, were employed for the carbon-carbon bond formation to connect the building blocks.
- Shikichi, Yasumasa,Mori, Kenji
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p. 1943 - 1951
(2013/01/15)
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- Total synthesis of a cuticular hydrocarbon from the cane beetle Antitrogus parvulus: Confirmation of the relative stereochemistry
-
The stereoselective reaction of an allyl bromide with an aldehyde mediated by a low valency bismuth species was the key reaction in stereoselective syntheses of (4S,6R,8R,10S,16S)- and (4S,6R,8R,10S,16R)-4,6,8,10,16- pentamethyldocosanes. 13C N
- Basar, Norazah B.,Liu, Hao,Negi, Devendra,Sirat, Hasnah M.,Morris, Gareth A.,Thomas, Eric J.
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supporting information; experimental part
p. 1743 - 1745
(2012/04/23)
-
- Copper-catalyzed cross-coupling reaction of organoboron compounds with primary alkyl halides and pseudohalides
-
Non-activated alkyl electrophiles, including alkyl iodides, bromides, tosylates, mesylates, and even chlorides, underwent copper-catalyzed cross-coupling with aryl boron compounds and alkyl 9-BBN reagents (see scheme; 9-BBN=9-borabicyclo[3.3.1]nonane). The reactions proceed with practically useful reactivities and thus complement palladium- and nickel-catalyzed Suzuki-Miyaura coupling reactions of alkyl halides.
- Yang, Chu-Ting,Zhang, Zhen-Qi,Liu, Yu-Chen,Liu, Lei
-
supporting information; experimental part
p. 3904 - 3907
(2011/05/15)
-
- Liposomal circular dichroism. assignment of remote stereocenters in plakinic acids K and L from a plakortis-xestospongia sponge association
-
"Figure Presented" Two new ωtu-phenyl polyketide peroxides, plakinic acids K and L, were isolated from a two-sponge association of Plakortis halichondroides and Xestospongia deweerdtae. The absolute configurations of the remote dimethyl-branched stereocenters in plakinic acid K were assigned by degradation of plakinic acid K to a long-chain naphthamide and analysis by liposomal circular dichroism (L-CD) and comparison with synthetic standards.
- Dalisay, Doralyn S.,Quach, Tim,Molinski, Tadeusz F.
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scheme or table
p. 1524 - 1527
(2010/06/20)
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- Composition of the cloacal gland secretion of tuatara, Sphenodon punctatus
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The lipophilic content of the cloacal gland secretion of the tuatara (Sphenodon punctatus) was investigated. GC/EI-MS Analysis of CH2Cl2 extracts of the secretions revealed triacylglycerols as major glandular constituents. Twelve major medium-chain fatty acids were found to be conjugated to glycerol in different combinations, resulting in complex mixtures. These acids were identified by transesterification and subsequent derivatization of natural samples, and their structures were verified by synthesis. The natural glycerides contain predominantly three of the following acids: octanoic (A), (E)- and (Z)-oct-4-enoic (B and C, resp.), (4E,6Z)-octa-4,6-dienoic (tuataric acid;D), (R)-2,6-dimethylheptanoic (E), (R)-2,6-dimethylhept-5-enoic (F), (Z)-dec-4-enoic (G), (4Z,7Z)-deca-4,7-dienoic (H), (R)-3,7-dimethyloct-6-enoic (I), (R)-4,8-dimethylnon-7-enoic (J), (2R,6S)-2,6,10-trimethylundec-9-enoic (K), and (2R,5E)-2,6,10-trimethylundeca-5,9-dienoic acids (L). Several additional acids, occurring in trace amounts only, were tentatively identified by MS. The elucidation of the absolute configuration of the acids was performed by GC on chiral phases. Individual tuatara show specific mixtures of glycerides with up to 100 components. The individual mixtures may permit individual recognition because the bouquets seem to be stable over years.
- Flachsbarth, Birte,Fritzsche, Matthias,Weldon, Paul J.,Schulz, Stefan
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experimental part
p. 1 - 37
(2010/04/23)
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- Synthesis and structure of phosphatidylinositol dimannoside
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(Chemical Equation Presented) (R)-Tuberculostearic acid (2) was synthesized in seven steps from (S)-citronellol (5). The carbon chain of 2 was assembled by copper-catalyzed cross coupling of (5)-citronellol tosylate (6) and hexylmagnesium bromide; subsequent ozonolysis and reaction with 6-benzyloxyhexylmagnesium bromide furnished alcohol 10. Functional group manipulation afforded (R)-2 in 49% overall yield from 5. DCC coupling of (R)-2 with 3-O-benzyl-1-O-palmitoyl-sn-glycerol (16), followed by hydrogenolytic removal of the benzyl group and treatment with benzyl bis(diisopropyl) phosphoramidite, afforded phosphoramidite 20. Tetrazole-mediated coupling of 20 with PIM1 head group 21 gave 22, and subsequent debenzylation afforded phosphatidylinositol mono-mannoside, PIM1 (23). Similarly, coupling of 20 and 24 and removal of the benzyl protecting groups gave PIM2 (1c). Both 23 and 1c have a clearly defined acylation pattern, which was confirmed by mass spectrometry, with sn-1 palmitoyl and sn-2 tuberculostearoyl groups on the glycerol moiety. Both 23 and 1c were shown to modulate the release of the pro-inflammatory cytokine, IL-12, in a dendritic cell assay.
- Dyer, Blake S.,Jones, Jeremy D.,Ainge, Gary D.,Denis, Michel,Larsen, David S.,Painter, Gavin F.
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p. 3282 - 3288
(2008/02/04)
-
- Total synthesis of papulacandin D
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A total synthesis of the antifungal agent papulacandin D is reported. The molecule is representative of a large class of C-aryl glycosides that exhibit significant antifungal activity. The synthetic strategy bifurcates the molecule into two nearly equal subunits, the arylglycoside and 18-carbon fatty acid side chain. The key strategic transformations are (1) the palladium catalyzed, organosilanolate-based cross-coupling of a protected glucal silanol and (2) a catalytic enantioselective allylation of a dienal using allyltrichlorosilane. The synthesis was accomplished in 31 steps overall from commercial starting materials to afford over 50 mg of the natural product. Copyright
- Denmark, Scott E.,Regens, Christopher S.,Kobayashi, Tetsuya
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p. 2774 - 2776
(2008/02/02)
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- Chemoselective and scalable preparation of alkyl tosylates under solvent-free conditions
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The improved method for the efficient tosylation of alcohols has been reported using two procedures (A and B). Procedure A: methanol, ethanol, benzyl alcohols, and valuable ethylene glycols can be converted into their corresponding alkyl tosylates in very fast, simple, and efficient grinding method using potassium carbonate as solid base. Other primary and secondary alcohols need to add potassium hydroxide to reaction mixture (procedure B). High selectivity of tosylation was observed for these two procedures. Scale up ability was found in this method even in 100 mmol of substrate. The present method is the example of solid-state tosylation using tosyl chloride, and is a green chemical process due to solvent-free conditions.
- Kazemi, Foad,Massah, Ahmad R.,Javaherian, Mohammad
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p. 5083 - 5087
(2008/02/01)
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- Ultrasound assisted synthesis of 5,9-dimethylpentadecane and 5,9-dimethylhexadecane - The sex pheromones of Leucoptera coffeella
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Racemic 5,9-dimethylpentadecane and 5,9-dimethylhexadecane, the major and minor constituents, respectively, of the sex pheromone of Leucoptera coffeella, have been synthesized from citronellol in 56-58% overall yield through six steps. Ultrasound irradiation efficiently supported tosylation of alcohols (two steps) as well as the subsequent cross coupling reactions with the pertinent Grignard reagents (also two steps).
- Doan, Nhuan Ngoc,Le, Thach Ngoc,Nguyen, Hao Cong,Hansen, Poul Erik,Duus, Fritz
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p. 2080 - 2088
(2008/02/08)
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- Synthesis of (4R,8R)- and (4S,8R)-4,8-dimethyldecanal: the common aggregation pheromone of flour beetles
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The synthesis of (4R,8R)- and (4S,8R)-4,8-dimethyldecanal 1 and 1a has been achieved connecting the chiral building block (R)-2-methyl-1-bromobutane 4 with (R)- and (S)-citronellol derivatives. The key intermediate 4 was obtained optically pure in five steps from methyl (S)-3-hydroxy-2-methylpropionate 2.
- Santangelo, Ellen M.,Corrêa, Arlene G.,Zarbin, Paulo H.G.
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p. 5135 - 5137
(2007/10/03)
-
- ISONITRILES AND ANTIFOULING AGENTS AGAINST THE ADHESION OF AQUATICS
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Isonitriles represented by the general formula (1) and antifouling agents against the adhesion of aquatics containing the same: (1) wherein R1 is CH2X (wherein X is hydroxy, halogeno, isocyano, amino, substituted amino, or optionally substituted, alkoxy, alkenyloxy, acyloxy, organosulfonyloxy, organosulfenyl, organosulfinyl, organosulfonyl, amido, or imido) or COOR4 (wherein R4 is optionally substituted, alkyl, alkenyl, or aralkyl); and R2 and R3 are each independently alkyl.
- -
-
Page/Page column 17-18
(2010/10/20)
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- Synthesis of the four stereoisomers of 7-acetoxy-15-methylnonacosane, a component of the female sex pheromone of the screwworm fly, Cochliomyia hominivorax
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The four stereoisomers of 7-acetoxy-15-methylnonacosane (1), a component of the female sex pheromone of the New World screwworm fly (Cochliomyia hominivorax) were synthesized. The stereogenic center at C-15 of 1 originated from that of the enantiomers of citronellal, and that at C-7 was generated by lipase-catalyzed asymmetric acetylation of (3RS,11R)- and (3RS,11S)-17-methyl-1- trimethylsilylpentacos-1-yn-3-ol (13). Three of the stereoisomers of 1 showed equivalent good pheromone activity, while the activity of (7R,15R)-1 was weak.
- Mori, Kenji,Ohtaki, Takashi,Ohrui, Hiroshi,Berkebile, Dennis R.,Carlson, David A.
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p. 1768 - 1778
(2007/10/03)
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- Syntheses of racemic and diastereomeric mixtures of 3,7,11,15- tetramethylhentriacontane and 4,8,12,16-tetramethyldotriacontane, the cuticular tetramethylalkanes of the tsetse fly, Glossina brevipalpis
-
Cuticular hydrocarbons of the tsetse fly, Glossina brevipalpis, contain 3,7,11,15-tetramethylhentriacontane and 4,8,12,16-tetramethyldotriacontane as possible candidates for its contact sex pheromone. These were synthesized as racemic and diastereomeric mixtures starting from racemic citronellol and employing phenylsulfone-mediated chain-elongation as the key reaction.
- Shibata, Chie,Furukawa, Ayako,Mori, Kenji
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p. 582 - 587
(2007/10/03)
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- Syntheses of female sex pheromone precursors of pine sawfly species and of some structurally related methyl-branched long-chain 2-alkanols.
-
3,7-Dimethyl-2-undecanol, 3,7,9-trimethyl-2-tridecanol, and 3,7, 11-trimethyl-2-tridecanol were synthesized as racemic mixtures in moderate yields. The alcohols are known precursors of the female sex pheromones of the pine sawfly species Diprion nipponica, Macrodiprion nemoralis, and Microdiprion pallipes, respectively. Stereoisomeric mixtures of 3,8,12-trimethyl-2-tridecanol, erythro-(2R,3R, 11R/S)-3,11-dimethyl-2-tetradecanol, 3,5-dimethyl-2-tetradecanol, and 5,7-dimethyl-2-tetradecanol, structurally related to sex pheromone alcohol precursors of pine sawfly species, were also synthesized in moderate yields. The key reaction in the syntheses was the ring opening of gamma-butyrolactones by using different alkyl lithiums as nucleophiles.
- Hedenstroem, Erik,Andersson, Fredrik
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p. 1237 - 1254
(2007/10/03)
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- Synthesis of the enantiomers of some methyl-branched cuticular hydrocarbons of the ant, Diacamma sp.
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The enantiomers of 3-methylpentacosane, 3-methylheptacosane, 3-methylnonacosane, 13-methylheptacosane, and 5-methylheptacosane were synthesized by starting from the enantiomers of 2-methylbutyl bromide or citronellol. These methyl-branched alkanes are the characteristic components of the cuticular hydrocarbons of queen of the ant, Diacamma sp.
- Marukawa, Kaoru,Takikawa, Hirosato,Mori, Kenji
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p. 305 - 314
(2007/10/03)
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- Syntheses of the sixteen stereoisomers of 3,7,11-trimethyl-2-tridecanol, including the (2S,3S,7S,11R) and (2S,3S,7S,11S) stereoisomers identified as pheromone precursors in females of the pine sawfly Microdiprion pallipes (Hymenoptera: Diprionidae)
-
All sixteen stereoisomers of 3,7,11-trimethyl-2-tridecanol were synthesised in high stereoisomerical purities (> 95%), for use in the identification of the stereoisomers present in females of the pine sawfly Microdiprion pallipes (Fallén) (Hymenoptera: Diprionidae) as the precursor of the actual sex pheromone (which is the propionate), and also for investigation of the biological activities of the esters. The key step in the syntheses was the coupling of each of the enantiomers of cis-3,4-dimethyl-γ-butyrolactone with each of the four pure stereoisomers of 1-lithio-2,6-dimethyloctanes. The four corresponding alcohols were obtained by lipase-catalysed (Amano PS) kinetic separation, based on selective acylation of either (2R/S,6S)- or (2R/S,6R)-2,6-dimethyl-1-octanol (obtained from the optically pure enantiomers of citronellal). Additionally, a mixture of the 16 possible stereoisomers of 3,7,11-trimethyl-2-tridecanol was also prepared. Wiley-VCH Verlag GmbH, 2001.
- Larsson, Michael,Nguyen, Ba-Vu,H?gberg, Hans-Erik,Hedenstr?m, Erik
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p. 353 - 363
(2007/10/03)
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- Absolute Configuration of a Ceramide with a Novel Branched-chain Fatty Acid Isolated from the Epiphytic Dinoflagellate, Coolia monotis
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The absolute configuration of the chiral center at the C15 position of a novel branched-chain fatty acid derived from a new ceramide isolated from the epiphytic dinoflagellate Coolia monotis was determined to be of R from by reversed-phase HPLC after clea
- Akasaka, Kazuaki,Shichijyukari, Seiya,Matsuoka, Shigeru,Murata, Michio,Meguro, Hiroshi,Ohrui, Hiroshi
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p. 1842 - 1846
(2007/10/03)
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- Synthesis of the spiroacetal parts of spirofungin A and B
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The C9-C20 spiroacetal parts of spirofungin A and B, antifungal antibiotics from Streptomyces violaceusniger Tu 4113, were synthesized simultaneously from (S)-citronellyl bromide and (±)-epoxy alcohol via alkyne-lactone coupling reaction and diastereomeric separation. (C) 2000 Elsevier Science Ltd.
- Shimizu, Yuko,Kiyota, Hiromasa,Oritani, Takayuki
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p. 3141 - 3144
(2007/10/03)
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- Synthesis and biological activity of methyl 2,6,10-trimethyldodecanoate and methyl 2,6,10-trimethyltridecanoate: Male-produced sexual pheromones of stink bugs Euschistus heros and Piezodorus guildinii
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Methyl 2,6,10-trimethyltridecanoate (1) and methyl 2,6,10-trimethyldodecanoate (2) have been identified as male-produced sex pheromones of the Brazilian soybean stink bugs Euschistus heros (F.) and Piezodorus guildinii (Westwood). In order to establish a defined attractive blend for both species, compounds 1 and 2 were synthesized as mixtures of stereoisomers to be employed in behavior bioassays. (±)-Citronellol (3) was utilized as starting material, and the syntheses was carried out in six steps with good overall yield. When tested alone, synthetic compounds 1 and 2 proved to be active in a two-choice olfactometer; however, a 20: 1 mixture of 1 and 2 was much more attractive to E. heros females. A similar blend had been found among the headspace volatiles of males.
- Zarbin, Paulo H. G.,Reckziegel, Aurelia,Plass, Ernst,Borges, Miguel,Francke, Wittko
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p. 2737 - 2746
(2007/10/03)
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- Simple Synthesis of 5,9-Dimethylated Long-Chain Alkanes, the Sex Pheromones of Leaf Miner Moths
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Each stereoisomeric mixture of 5,9-dimethylpentadecane and 5,9-dimethylhexadecane, the major and the minor sex pheromone components of Perileucoptera coffeella, respectively, was synthesized in about 25% overall yield through 6 steps from β-citronellol. 5
- Liang, Ting,Kuwahara, Shigefumi,Hasegawa, Morifumi,Kodama, Osamu
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p. 2474 - 2477
(2007/10/03)
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- Pheromone synthesis, CXCIX([≠]). Synthesis of all the stereoisomers of 7-methylheptadecane and 7,11-dimethylheptadecane, the female sex pheromone components of the spring hemlock looper and the pitch pine looper
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All the stereoisomers of 7-methylheptadecane (1) and 7,11- dimethylheptadecane (2) were synthesized by starting from the enantiomers of citronellol (3) and methyl 3-hydroxy-2-methylpropanonate (8), respectively. A short synthesis of meso-7,11-dimethylheptadecane [(7R, 11S)-2] was achieved starting from meso-2,6-dimethylheptanedioic acid [(2R,6S)21]. A mixture of (S)-1 and (7R, 11S)-2 is the pheromone of the spring hemlock looper moth (Lambdina athasaria) and the pitch pine looper moth (L. pellucidaria).
- Shirai, Yasuo,Seki, Masanori,Mori, Kenji
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p. 3139 - 3145
(2007/10/03)
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- Pheromone synthesis, CXCIV. - Synthesis of the enantiomers of (Z)-21- methyl-8-pentatriacontene, the major component of the female-produced contact sex pheromone of the yellow-spotted longicorn beetle, Psacothea hilaris
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Both the enantiomers of (Z)-21-methyl-8-pentatriacontene (1), the major component of the female-produced contact sex pheromone of the yellow-spotted longicorn beetle (Psacothea hilaris), were synthesized by starting from the enantiomers of citronellol (2).
- Domon, Kenji,Takikawa, Hirosato,Mori, Kenji
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p. 981 - 984
(2007/10/03)
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- Pheromone synthesis, CLXXIV: Synthesis of (5R,11S)-5,11-Dimethylheptadecane and (S)-2,5-Dimethylheptadecane, the major and the minor components of the sex pheromone of the geometrid moth, Lambdina fiscellaria lugubrosa
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(5R,11S)-5,11-Dimethylheptadecane (1), the major component of the female-produced sex pheromone of the western hemlock looper (Lambdina fiscellaria lugubrosa), was synthesized by starting from the enantiomers of methyl 3-hydroxy-2-methylpropanoate (3). (S)-2,5-Dimethylheptadecane (2), the minor and synergistic component of the pheromone, was also synthesized by starting from (S)-citronellol (4). VCH Verlagsgesellschaft mbH, 1996.
- Mori, Kenji,Horikiri, Hiromasa
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p. 501 - 505
(2007/10/03)
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- Pheromone Synthesis, CLXXVI: Synthesis of the four stereoisomers of 3,13-dimethylheptadecane, the major sex pheromone component of the western false hemlock looper
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All of the four stereoisomers of 3,13-dimethylheptadecane (1), the female-produced sex pheromone of the western false hemlock looper (Nepytia freemani), were synthesized by starting from the enantiomers of citronellol (2a) and 2-methyl-1-butanol (4a). VCH Verlagsgesellschaft mbH, 1996.
- Takikawa, Hirosato,Shirai, Yasuo,Kobayashi, Makoto,Mori, Kenji
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p. 1965 - 1970
(2007/10/03)
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- Synthesis of sphingosine relatives, XVIII: Synthesis of penazetidine A, an alkaloid inhibitor of protein kinase C isolated from the marine sponge Penares sollasi
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Two stereoisomers of penazetidine A (1a), the azetidine alkaloid isolated from the Indo-Pacific marine sponge Penares sollasi, were synthesized by starting from (S)-serine and (R)-or (S)-citronellol. The natural penazetidine A must be either (2S,3R,4S,12′
- Yajima, Arata,Takikawa, Hirosato,Mori, Kenji
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p. 1083 - 1089
(2007/10/03)
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- Pheromone Synthesis, CXLIX. Synthesis of (2E,4E,6R,10S)-4,6,10-Trimethyl-2,4-dodecadien-7-one - the Major Component of the Sex Pheromone of the Maritime Pine Scale (Matsucoccus feytaudi) - and its Three Stereoisomers
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(2E,4E,6R,10S)-4,6,10-Trimethyl-2,4-dodecadien-7-one (1) - the major component of the sex pheromone of the maritime pine scale - and its three stereoisomers were synthesized by starting from (R)- or (S)-citronellol (4) and employing the asymmetric epoxidation (9 -> 10) and the palladium-catalyzed reductive cleavage of the epoxy ring (13 -> 14) as the key steps.Key Words: Asymmetric epoxidation / 2,4-Dodecadien-7-one, 4,6,10-trimethyl / Maritime pine scale / Matsucoccus feytaudi / Pheromones
- Mori, Kenji,Harashima, Susumu
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p. 391 - 402
(2007/10/02)
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- Synthesis of (2E,4E,6R,10R)-4,6,10,12-Tetramethyl-2,4-tridecadien-7-one (Matsuone) - the Primary Component of the Sex Pheromone of Three Matsucoccus Pine Bast Scales - and Its Antipode
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(2E,4E,6R,10R)-4,6,10,12-Tetramethyl-2,4-tridecadien-7-one (1; matsuone) - the primary component of the sex pheromone of the red pine scale (Matsucoccus resinosae) and two other pine scales - and its antipode were synthesized by starting from (R)- or (S)-
- Mori, Kenji,Harashima, Susumu
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p. 993 - 1002
(2007/10/02)
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- Sonochemistry of Epoxyalkylhalides in the Presence of a Zinc-Copper Couple
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Under sonication in aqueous ethanol, a zinc-copper induces the conjugated addition of epoxyalkyl groups to electron deficient alkenes in synthetically useful yields, provided that the two reducible functionalities are sufficiently far apart; 3,4-epoxyalky
- Sarandeses, Luis A.,Mourino, Antonio,Luche, Jean-Louis
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p. 798 - 799
(2007/10/02)
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- Products Active on Mosquitoes: Part III - Synthesis of Biologically Active 3,7-Dimethyl-6-octene-1,8-diol Diethers
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Mixed diethers (IIIa-s) have been prepared from 8-hydroxy-monoethers (IIa-g) which in turn have been obtained from citronellyl ethers (Ia-g) by selenium oxidation.Most of the diethers are oviposition deterrent, while some of them also show inhibition towards the development of mosquitoes.
- Phadnis, A. P.,Nanda, B.,Patwardhan, Sarita A.,Powar, P.,Sharma, R. N.
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p. 867 - 870
(2007/10/02)
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- Insect Growth Regulators. XVII. Syntheses of Ethyl (E)- and (Z)-3,7,11-Trimethyl-11-chloro-10-oxo-2-dodecenoates and Aryl 3,7-Dimethyl-7-chloro-6-octanon-1-yl Ethers
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Starting from citronellol, four new juvenoids with the α-chloroketone system have been synthesized.These compounds exhibited low juvenile activity against Dysdercus cingulatus and Tenebrio molitor.
- Derdzinski, Krzysztof,Zabza, Andrzej
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p. 217 - 224
(2007/10/02)
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- Synthese von optisch aktiven Trogoderma-Pheromonen durch Kolbe-Elektrolyse
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The (R)-(-)-enantiomers of (Z)- (1) and (E)-14-methyl-8-hexadecen-1-ol (2) have been synthesized by coelectrolysis of (R)-(-)-4-methylhexanoic acid (7) with 12-(tetrahydro-2-pyranyloxy)-4-dodecynoic acid (8) and its subsequent hydrogenation.The acid 7 was prepared in high optical purity from (S)-(-)-citronellol (3) by conversion of the hydroxyl group to a methyl substituent and subsequent cleavage of (R)-(-)-2,6-dimethyl-2-octene (4) with ozone.By alkylation of 4-pentynoic acid (5) with 1-bromo-7-(tetrahydro-2-pyranyloxy)heptane (6) the alkynoic acid 8 was synthesized.
- Jensen, Uta,Schaefer, Hans-J.
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p. 292 - 297
(2007/10/02)
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- Novel benzofuranyl pest retardants
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Alkyl ethers of 2,3-dihydrobenzofuran where the alkyl chain may contain branched chains, unsaturated bonds, epoxy bridges, and may be substituted with halo, alkoxy, lower alkenyloxy, or lower alkynyloxy substituents useful in killing and preventing the proliferation of insects and other pests by upsetting their hormone balance.
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