- A new stereocontrolled, pyrylium-based route to conjugated dienynes: The first synthesis of Carduusyne A
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A new stereocontrolled route to conjugated dienynes is described, utilising organometallic addition to pyrylium salts followed by Wittig homologation and dehydrohalogenation. The utility of this methodology is illustrated in the first total synthesis of the marine metabolite Carduusyne A.
- Charoenying, Patchanee,Huw Davies,McKerrecher, Darren,Taylor, Richard J. K.
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Read Online
- Stereoselective synthesis of C3–C17 and C18–C34 subunits of bullatanocin utilizing α-chloro sulfide intermediates
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A convergent synthesis of bullatanocin is envisaged by the union of C18–C34, C3–C17 and the butenolide subunits. The synthesis of the C3–C17 and C18–C34 subunits is disclosed that takes advantage of the chirality of tartaric acid for 1,2-asymmetric induct
- Chowhan, L. Raju,Raghavan, Sadagopan
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Read Online
- Enzyme kinetics and inhibition of histone acetyltransferase KAT8
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Lysine acetyltransferase 8 (KAT8) is a histone acetyltransferase (HAT) responsible for acetylating lysine 16 on histone H4 (H4K16) and plays a role in cell cycle progression as well as acetylation of the tumor suppressor protein p53. Further studies on its biological function and drug discovery initiatives will benefit from the development of small molecule inhibitors for this enzyme. As a first step towards this aim we investigated the enzyme kinetics of this bi-substrate enzyme. The kinetic experiments indicate a ping-pong mechanism in which the enzyme binds Ac-CoA first, followed by binding of the histone substrate. This mechanism is supported by affinity measurements of both substrates using isothermal titration calorimetry (ITC). Using this information, the KAT8 inhibition of a focused compound collection around the non-selective HAT inhibitor anacardic acid has been investigated. Kinetic studies with anacardic acid were performed, based on which a model for the catalytic activity of KAT8 and the inhibitory action of anacardic acid (AA) was proposed. This enabled the calculation of the inhibition constant Ki of anacardic acid derivatives using an adaptation of the Cheng-Prusoff equation. The results described in this study give insight into the catalytic mechanism of KAT8 and present the first well-characterized small-molecule inhibitors for this HAT.
- Wapenaar, Hannah,Van Der Wouden, Petra E.,Groves, Matthew R.,Rotili, Dante,Mai, Antonello,Dekker, Frank J.
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- Stereoselective Synthesis of Perfluoroalkylated (E,E)-Dienes from Perfluoroalkylated Alkynes. The Synthesis of Fluorinated Analogs of Lepidoptera Pheromones
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Pd(dba)2 -HOAc catalyzed the isomerization of 1-perfluoroalkyl-1-alkynes to give 1-perfluoroalkyl-(1E,3E)-dienes in good yield and stereoselectivity; the fluorinated analogs of Lepidoptera species sex pheromone attractants were synthesized applying this method.
- Wang, Zhong,Lu, Xiyan
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Read Online
- Chemoproteomic profiling reveals cellular targets of nitro-fatty acids
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Nitro-fatty acids are a class of endogenous electrophilic lipid mediators with anti-inflammatory and cytoprotective effects in a wide range of inflammatory and fibrotic disease models. While these beneficial biological effects of nitro-fatty acids are mainly attributed to their ability to form covalent adducts with proteins, only a small number of proteins are known to be nitro-alkylated and the scope of protein nitro-alkylation remains undetermined. Here we describe the synthesis and application of a clickable nitro-fatty acid probe for the detection and first global identification of mammalian proteins that are susceptible to nitro-alkylation. 184 high confidence nitro-alkylated proteins were identified in THP1 macrophages, majority of which are novel targets of nitro-fatty acids, including extended synaptotagmin 2 (ESYT2), signal transducer and activator of transcription 3 (STAT3), toll-like receptor 2 (TLR2), retinoid X receptor alpha (RXRα) and glucocorticoid receptor (NR3C1). In particular, we showed that 9-nitro-oleate covalently modified and inhibited dexamethasone binding to NR3C1. Bioinformatic analyses revealed that nitro-alkylated proteins are highly enriched in endoplasmic reticulum and transmembrane proteins, and are overrepresented in lipid metabolism and transport pathways. This study significantly expands the scope of protein substrates targeted by nitro-fatty acids in living cells and provides a useful resource towards understanding the pleiotropic biological roles of nitro-fatty acids as signaling molecules or as multi-target therapeutic agents.
- Fang, Ming-Yu,Huang, Kuan-Hsun,Tu, Wei-Ju,Chen, Yi-Ting,Pan, Pei-Yun,Hsiao, Wan-Chi,Ke, Yi-Yu,Tsou, Lun K.,Zhang, Mingzi M.
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- IMMUNOTHERAPEUTIC AGENT
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Compounds for use in the treatment of sepsis and/or the prevention or treatment of post-sepsis syndrome.
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Paragraph 0101-0102
(2018/07/29)
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- Asymmetric Total Synthesis of Distaminolyne A and Revision of Its Absolute Configuration
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The first total synthesis of a marine derived polyacetylene, distaminolyne A, and its enantiomer were achieved from the commercially available undec-10-en-1-ol. A key proline-catalyzed asymmetric α-aminooxylation of an aldehyde intermediate was used to in
- Sun, Dong-Yu,Han, Guan-Ying,Gong, Jing-Xu,Nay, Bastien,Li, Xu-Wen,Guo, Yue-Wei
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supporting information
p. 714 - 717
(2017/02/10)
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- Enantioselective Rhodium-Catalyzed Atom-Economical Macrolactonization
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A highly attractive route toward macrolactones, which form the cyclic scaffold of a multitude of diverse natural compounds, is described. Although many chemical approaches to this structural motif have been explored, an asymmetric variant of the cyclization is unprecedented. Herein we present an enantioselective macrolactonization through an intramolecular atom-economical rhodium-catalyzed coupling of ω-allenyl-substituted carboxylic acids. The use of a modified diop ligand, chiral DTBM-diop, led to high enantioselectivity (up to 93 % ee). The reaction tolerated a large variety of functionalities, including α,β-unsaturated carboxylic acids and depsipeptides, and provided the desired macrocycles with very high enantio- and diastereoselectivity.
- Ganss, Stephanie,Breit, Bernhard
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supporting information
p. 9738 - 9742
(2016/08/10)
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- In situ proteome profiling of C75, a covalent bioactive compound with potential anticancer activities
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A library of cell-permeable, minimally tagged C75 analogues was synthesized and used to uncover biological targets in human liver cancer cells. Known targets of C75, namely FASN and CPT1A, together with other unknown targets, including PDIA3, TFRC, and GAPDH, were thus identified.
- Cheng, Xiamin,Li, Lin,Uttamchandani, Mahesh,Yao, Shao Q.
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supporting information
p. 1414 - 1417
(2014/04/03)
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- Triphenylene discotic liquid crystal trimers synthesized by Co 2(CO)8-catalyzed terminal alkyne [2 + 2 + 2] cycloaddition
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The synthesis of star-shaped discotic liquid crystal trimers using Co 2(CO)8-catalyzed terminal alkyne [2 + 2 + 2] cycloaddition reaction is reported. The trimers consist of three triphenylene discotic units linked to a central 1,2,4-trisubstituted benzene ring via flexible spacers. The trimers were synthesized in the yields up to 70% by mixing the monomers with 10 mol % of Co2(CO)8 as the catalyst in refluxing 1,4-dioxane. The liquid crystalline properties were investigated by using polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). Trimer 4 with an ester connecting group and a longer spacer exhibited a rectangular columnar mesophase, while 5b and 5c possessing an ether linkage and a shorter spacer display a hexagonal columnar mesophase. The connecting functional group and the length of the flexible spacer between the central benzene ring and the triphenylene units have pivotal influence on the mesomorphism.
- Han, Bin,Hu, Ping,Wang, Bi-Qin,Redshaw, Carl,Zhao, Ke-Qing
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p. 2852 - 2861
(2014/01/06)
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- Tetris in monolayers: Patterned self-assembly using side chain shape
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The "kinked" shapes of conjugated alkadiynes constrain chain packing in monolayers on HOPG. Centrally located diyne units permit assembly of 1,5-bis(alkadiyne)anthracene monolayers. Off-center diynes inhibit self-assembly. Shape matched pairs of off-center diyne chains direct self-assembly of compositionally patterned, two component monolayers.
- Xue, Yi,Zimmt, Matthew B.
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supporting information; experimental part
p. 8832 - 8834
(2011/09/16)
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- HETEROCYCLIC DERIVATIVES THAT ARE USED IN THE TREATMENT OF NEURODEGENERATIVE DISEASES
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The present invention relates to compounds of Formula (I) below, to their pharmaceutically acceptable salts and to their isomers or mixtures of isomers: HetAr—X—CHR1R2 (I) in which: -HetAr represents a group chosen from: —X represents a linear, saturated or unsaturated, hydrocarbon-based chain comprising from 8 to 22 carbon atoms, optionally interrupted by an —NH— or —NH—CO— group, —R1 represents a hydrogen atom or an —OH, —O(C1-C6)alkyl, —OCO((C1-C6)alkyl), —OSO2((C1-C6)alkyl) or —OSO3H group, and —R2 represents a hydrogen atom or a (C2-C6)alkynyl, (C2-C6)alkenyl or (C3-C6)cycloalkyl group. The present invention also relates to a process for preparing the compounds of Formula (I), and also to the use thereof, especially in the treatment of neurodegenerative diseases.
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(2011/06/10)
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- Phase separation as a strategy toward controlling dilution effects in macrocyclic glaser-hay couplings
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Macrocycles are abundant in numerous chemical applications, however the traditional strategy for the preparation of these compounds remains cumbersome and environmentally damaging; involving tedious reaction set-ups and extremely dilute reaction media. The development of a macrocyclization strategy conducted at high concentrations is described which exploits phase separation of the catalyst and substrate, as a strategy to control dilution effects. Sequestering a copper catalyst in a highly polar and/or hydrophilic phase can be achieved using a hydrophilic ligand, T-PEG1900, a PEGylated TMEDA derivative. Similarly, phase separation is possible when suitable copper complexes are soluble in PEG400, a green and efficient solvent which can be utilized in biphasic mixtures for promoting macrocyclization at high concentrations. The latter phase separation technique can be exploited for the synthesis of a wide range of industrially relevant macrocycles with varying ring sizes and functional groups.
- Bedard, Anne-Catherine,Collins, Shawn K.
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supporting information; experimental part
p. 19976 - 19981
(2012/01/13)
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- Mn(0)-mediated chemoselective reduction of aldehydes. Application to the synthesis of α-deuterioalcohols
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A mild, simple, safe, chemoselective reduction of different kinds of aldehydes to the corresponding alcohols mediated by the Mn dust/water system is described. In addition to this, the use of D2O leads to the synthesis of α-deuterated alcohols and constitutes an efficient, inexpensive alternative for the preparation of these compounds.
- Jimenez, Tania,Barea, Elisa,Oltra, J. Enrique,Cuerva, Juan M.,Justicia, Jose
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experimental part
p. 7022 - 7025
(2010/11/18)
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- Total synthesis of clathculins A and B
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Clathculins A and B represent a new class of vic-diamine alkaloids containing a PA2 unit as the basic structure. We report the first total syntheses of 1 and 2, which confirm the assigned structure of each. Dependence of their NMR spectroscopic behavior a
- Hoye, Rebecca C.,Anderson, Gretchen L.,Brown, Susan G.,Schultz, Erica E.
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experimental part
p. 7400 - 7403
(2011/02/22)
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- ANTIBACTERIAL AGENTS
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Compounds of formula (I) have antibacterial activity wherein R represents hydrogen or 1, 2 or 3 optional substituents; W is =C(R1)- or =N-; R1 is hydrogen or an optional substituent and R2 is hydrogen, methyl, or fluorine; or R1 and R2 taken together are -CH2-, -CH2CH2-, -O-, or, in either orientation, -O- CH2- Or -OCH2CH2-; R3 is a radical of formula -(Alk1)m-(Z)p-(Alk2)n-Q wherein m, p and n are independently 0 or 1, provided that at least one of m, p and n is 1, Z is -O-, -S-, -S(O)-, -S(O2)-, -NH-, -N(CH3)-, -N(CH2CH3)-, -C(=O)-, -O-(C=O)-, -C(=O)-O-, or an optionally substituted divalent monocyclic carbocyclic or heterocyclic radical having 3 to 6 ring atoms; or an optionally substituted divalent bicyclic heterocyclic radical having 5 to 10 ring atoms; Alk1 and Alk2 are optionally substituted C1C6 alkylene, C2-C6 alkenylene, or C2-C6 alkynylene radicals, which may optionally terminate with or be interrupted by -O-, -S-, -S(O)-, -S(O2)-, -NH-, -N(CH3)-, or -N(CH2CH3)-; and Q is hydrogen, halogen, nitrile, or hydroxyl or an optionally substituted monocyclic carbocyclic or heterocyclic radical having 3 to 6 ring atoms; or an optionally substituted bicyclic heterocyclic radical having 5 to 10 ring atoms.
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(2010/11/28)
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- IMMUNOTHERAPEUTIC AGENT
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The invention relates to a compound which is an ester of 1, 2, 3-propanetriol with one or more C11 to C24 fatty acids, wherein at least one fatty acid has at least one double bond. The compound is useful in the treatment of chronic inflammatory disorders.
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(2008/06/13)
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- Silver(I)-catalysed protiodesilylation of 1-(Trimethylsilyl)-1-alkynes
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A procedure for protiodesilylation of 1-(trimethylsilyl)-1-alkynes that involves the use of catalytic amounts of AgNO3 and does not require the employment of KCN is described. This procedure allows for chemoselective deprotection of 1-(trimethylsilyl)-1-alkynes containing α-(trimethylsilyl) benzyl moieties, tert-butyldiphenylsilyl alkyl ethers or tert-butyldimethylsilyl aryl ether groups. However, it causes complete desilylation of l-(trimethylsilyl)-1-alkynes characterised by a primary alcoholic group protected as a tert-butyldimethylsilyl ether. Interestingly, compounds that contain this last functional group can also furnish the corresponding alcohols by treatment with a catalytic amount of aqueous HNO3. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.
- Carpita, Adriano,Mannocci, Luca,Rossi, Renzo
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p. 1859 - 1864
(2007/10/03)
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- Preparation and cancer cell invasion inhibitory effects of C16-alkynic fatty acids.
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Five C(16)-alkynic fatty acids (2-6) were prepared and examined their inhibitory effects on cancer cell invasion. It has been found that hexadeca-6,8,10-triynoic acid (5) and hexadeca-8,10,12-triynoic acid (6) exhibit similar potent inhibitory activities with that of octadeca-8,10,12-triynoic acid (1) which was isolated from Scurrula atropurpurea (Loranthaceae).
- Ohashi, Kazuyoshi,Winarno, Hendig,Mukai, Mutsuko,Shibuya, Hirotaka
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p. 463 - 466
(2007/10/03)
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- Study of the regioselectivity in the hydrotelluration of hydroxy alkynes
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Vinylic tellurides were synthesized by the addition of organotellurols to acetylenic alcohols and the regioselectivity of the reaction was evaluated.
- Stefani, Hélio A.,Cardoso, Lincoln D. G.,Valduga, Claudéte J.,Zeni, Gilson
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p. 167 - 172
(2007/10/03)
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- Stereospecific synthesis of (E,Z)- and (Z,Z)-hexadeca-10,12-dienal. Sex pheromone components of Diaphania hyalinata
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Isomeric (E,Z)- and (Z,Z)-hexadeca-10,12-dienal were prepared, stereospecifically, in 51% and 43% overall yields from dec-1-yne.
- Cabezas, Jorge A.,Oehlschlager, Allan C.
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p. 107 - 111
(2007/10/03)
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- An Efficient Derivation of the Versatile Chiron Antipode 1-tert-Butyldimethylsilylpenta-1,4-diyn-3-ol: Application to the Synthesis of (15E,R,R)-Duryne
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The title chiron, 1-tert-butyldimethylsilylpenta-1,4-diyn-3-ol (5), an essential segment of various bioactive polyacetylenic alcohols, has been efficiently resolved via a lipase-catalyzed acylation strategy. Lipases from different Pseudomonas species and Candida rugosa (CRL) furnished its (S)-antipode (as esters) with 86-96% ee. However, the (R)-alcohol 5 could be prepared with acceptable enantiomeric purity (93% ee) only using CRL-vinyl acetate-diisopropyl ether as the reagent protocol and under double filtration conditions. The chiron alcohol was then extended to the target compound (15E,R,R)-duryne (I) by its pyranylation, alkylation with the required achiral C20-α,ω-dibromide 15, and suitable functionalization.
- Sharma,Chattopadhyay
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p. 6128 - 6131
(2007/10/03)
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- Synthesis of (3Z,13Z)-3,13-octadecadienyl acetate - Sex pheromone of Synanthedon tenuis-using readily available C11-synthon
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Synthesis of (3Z,13Z)-3,13-octadecadienyl acetate has been achieved from the readily available 10-undecen-1-ol using cheaper reagents and less number of steps. In the key step alkylation of an alkyne is performed with solid sodamide giving the product in 50% yield. The method can be easily scaled-up.
- Narasimhan,Ganeshwar Prasad,Madhavan
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- Synthesis of dodec-10E-Enyl acetate - The sex pheromone of phyllonorycter blancardella (Lepidoptera: Gracillariidae)
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Dodec-10E-enyl acetate has been synthesized from undecenoic acid. Field trials have shown its high attractiveness for Phyllonorycter blancardella males. 1996 Plenum Publishing Corporation.
- Ishchenko
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- An Inexpensive Air-Stable Titanium-Based System for the Conversion of Esters to Primary Alcohols
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Polymethylhydroxiloxane, when combined with titanium(IV) isopropoxide, provides a convenient system for the conversion of esters to the corresponding primary alcohols in the presence of a wide range of functional groups.Reactions are carried out as mixtures of the neat reaction components; workup with aqueous alkaline THF affords primary alcohols in good to excellent yields.The system tolerates primary alkyl bromides and iodides, olefins, epoxides, and alkynes.Steric differentiation of methyl and tert-butyl esters is also possible.The results observed in the parent and related reactions argue against pathways involving Lewis-acid catalysis and anionic hydridosilicate-mediated reductions, and instead support a neutral titanium hydride complex or strongly associated titanium/silane complex as the active reducing agent.
- Reding, Matthew T.,Buchwald, Stephen L.
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p. 7884 - 7890
(2007/10/03)
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- A simple, cost effective synthesis of E,Z-2,13-octadecadienyl acetate, a major sex pheromone component of lepidopteran pests
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A simple, cost effective synthesis of E,Z-2,13-octadecadienyl acetate (1), a major sex pheromone component of many lepidopteran pests, has been achieved in optimum number of steps using cheaper raw meterials.The strategy provides the target compound in 43percent overall yield, and can be scaled up easily.
- Narasimhan, S.,Mohan, H.,Madhavan, S.
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p. 531 - 534
(2007/10/02)
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- Total synthesis of (10Z,13Z,16Z)-nonadeca-10,13,16,18-tetraen-1-ol
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The title compound is obtained by successive couplings between propargylic bromides and alkynes, which are catalyzed by cuprous salts.Key Words: 1-4 diyne / coupling / hydroboration / Z,Z,Z-triene
- Crousse, B.,Pichon, O.,Soulie, J.
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p. 154 - 159
(2007/10/02)
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- An Air-Stable Catalyst System for the Conversion of Esters to Alcohols
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The combination of 5 mol percent of Ti(O-i-Pr)4 with 2.5-3.0 equiv (EtO)3SiH cleanly hydrosilylates esters to silyl ethers at 40-55 deg C, which can be converted to the corresponding primary alcohols via aqueous alkaline hydrolysis in excellent overall yield.The reaction can be carried out in the air, without solvent, and displays a high level of functional group compatibility.
- Berk, Scott C.,Buchwald, Stephen L.
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p. 3751 - 3753
(2007/10/02)
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- Synthesis of (E,E)-10,12-hexadecadienal and (Z)-11-octadecenal
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Two economically important insect pheromones, viz. (E,E)-10,12-hexadecadien-1-al (1) and (Z)-11-octadecenal (2) of cotton pests have been synthesised from cheap and readily available materials utilising in situ alkylation of dianion of 4-pentyn-1-ol obtainable easily by lithium amide induced opening of tetrahydrofurfuryl chloride in liquid ammonia.
- Yadav, J. S.,Balakrishnan, Kamalam,Sivadasan, Latha
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p. 297 - 302
(2007/10/02)
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- Improved syntheses of hydroxy acid precursors of macrolide pheromones of cucujid grain beetles
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Syntheses of 11- and 12-hydroxy-(Z)-3-dodecenic, 11- and 12-hydroxy-(Z,Z)-3,6-dodecadienic, and 13-hydroxy-(Z,Z)-5,8-tetradecadienic acids are reported.These unsaturated hydroxy acids are precursors of male-produced macrolide aggregation pheromones of grain beetles of the genera Cryptolestes and Oryzaephilus.The sequence of reactions for synthesis of the hydroxy-(Z)-3 acids was carboxylation of the dilithium salt of 10- or 11-hydroxy undecyne, deconjugation of the resulting carboxylic acids with NaNH2 in THF/liquid ammonia to a mixture of 2,3-allenic and 3-alkynoic acids, and hydrogenation of the mixture with P-2 nickel catalyst.This latter reaction gave only the desired hydroxy-(Z)-3-alkenoic acids.The convergent point in the syntheses of the diunsaturated hydroxy-(Z,Z) acids was the coupling of the dimagnesium salt of 3-butyn-1-ol or 5-hexyn-1-ol to the appropriate functionalized propargylic bromide.The resulting 1,4-diacetylenic alcohols were oxidized with Jones reagent to the corresponding carboxylic acids, which were hydrogenated over P-2 nickel catalyst and deprotected.
- Oehlschlager, A. C.,Czyzewska, E.,Aksela, R.,Pierce, H. D.
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p. 1407 - 1413
(2007/10/02)
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- SIMPLE AND STEREOCONTROLLED SYNTHESIS OF AN OPTIMAL ISOMERIC MIXTURE OF 3,13-OCTADECADIEN-1-YL ACETATES
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A simple route has been developed for the preparation of the optimal isomeric mixture of 3,13-octadecadien-1-yl acetates (ODDA) which is the active sex pheromone of many Synanthedon species.The stereocontrolled formation of double bonds have been achieved via Wittig reaction and subsequent reduction of C-C triple bond.
- Vinczer, Peter,Baan, Gabor,Juvancz, Zoltan,Novak, Lajos,Szantay, Csaba
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p. 1257 - 1270
(2007/10/02)
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- PROTOTROPIC ISOMERIZATION OF ACETYLENIC HYDROCARBONS AND ALCOHOLS UNDER THE INFLUENCE OF LITHIUM 2-AMINOETHYLAMIDE IN ETHYLENEDIAMINE
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The system containing lithium 2-aminoethylamide in ethylenediamine is an effective system for the production of acetylenic hydrocarbons and alcohols with a terminal triple bond.As a result of prototropic isomerization in this system 5-dodecyne, 4-tridecyne, 7-tetradecyne, 2-heptyn-1-ol, 2-nonyn-1-ol, and 2-undecyn-1-ol gave high yields of the corresponding isomers with a terminal triple bond, i.e., 1-dodecyne, 1-tridecyne, 1-tetradecyne, 6-heptyn-1-ol, 8-nonyn-1-ol, and 10-undecyn-1-ol.The synthesis of the long-chain alcohol 8,10-heneicosadiyn-1-ol was realized from the compounds containing a triple bond.
- Remizova, L. A.,Kryukov, A. V.,Balova, I. A.,Favorskaya, I. A.
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p. 909 - 912
(2007/10/02)
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- Metamorphosis of Castor Oil to Insect Sex-pheromones and Useful Synthons
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The primary fragmentation products of Castor oil (1), namely, methyl undec-10-enoate (2) and sebacic acid (3) have been converted, using novel reactions and strategies into synthons of the type H-CC-(CH2)n-3-CH2OTHP (n=6=4; n=7=14; n=8=22; n=9=29).A surprisingly clean decarboxylative elimination of sebacic acid monoester gives methyl non-8-enoate (7), a synthon related to recefeiolide and a precursor to 4, the utility of which, has been illustrated with the synthesis of insect-pheromones of the species Grapholita molesta.Methyl dec-9-enoate (15) has been prepared by a novel and practical terminal ? to lower terminal ? degradation of 2.Compound 7 has been transformed via synthon 14 to the insect sex-pheromones of the species, Spodoptera frugiperda, Heliothis virescens and Paralobesia viteana in high yields and excellent stereochemical purity. 1-Tetrahydropyranyloxyundec-10-yne (22) readily prepared from 2, has been used to illustrate a new strategy in pheromone synthesis, namely, the use of coupling elements, leading to the preparation of bombykol in high yields and excellent stereochemical purity. 1-Tetrahydropyranyloxydodec-11-yne (29), already reported, has been transformed to vaccenic acid (30), the transposed ?-isomer of oleic acid, in good yields, thus demonstrating the use of acetylide synthons for the preparation of rare fatty acids also.
- Ranganathan, S.,Maniktala, Vibha,Kumar, Raaj,Singh, G. P.
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p. 1197 - 1207
(2007/10/02)
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- (E,Z)-2,13-OCTADECADIEN-1-OL ACETATE. A NEW FEROMONE STRUCTURE FOR SESIID MOTHS
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(E,Z)-2,13-Octadecadien-1-ol acetate was identified from ovipositor extracts of the grape root borer and was shown to attract males of the species.
- Schwarz, Meyer,Klun, J. A.,Leonhardt, B. A.,Johnson, D. T.
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p. 1007 - 1010
(2007/10/02)
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- Synthesis of (Z,Z)-11,13-Hexadecadienal, a Principal Component of Navel Orangeworm (Pamyelois transitella) Pheromone
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This report outlines a commercial synthetic process for (Z,Z)-11,13-hexadecadienal (navel orangeworm pheromone).The synthetic scheme which is employed introduces the stereochemically labile conjugated diene moiety at a late stage in the synthesis, thereby avoiding complications during the purification of intermediates.In addition, the aldehyde function is generated through a Grignard reaction sequence, obviating the generally accepted techniques which are usually unsuitable for commercial preparations.We have also observed the first reported selective inclusion by urea of a conjugated (Z,Z)-diene as a means of mild purification of labile dienic pheromone intermediates.
- Bishop, Clyde E.,Morrow, Gary W.
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p. 657 - 660
(2007/10/02)
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- Some Soluble Polydiacetylenes Derived from 10,12-Docosadiyn-1,22-diol
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Synthesis and physical properties of some new soluble polydiacetylenes ontained by solid state polymerization of derivatives of 10,12-Docosadiyn-1,22-diol (1) are described.
- Plachetta, Christoph,Rau, Norbert Otto,Schulz, Rolf C.
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p. 141 - 152
(2007/10/02)
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- NEW STEREOSPECIFIC SYNTHESES OF PHEROMONE BOMBYKOL AND ITS THREE GEOMETRICAL ISOMERS
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We describe stereospecific syntheses of pheromone, bombykol and the three geometrical isomers by means of the palladium-catalyzed cross-coupling between an appropriate alkenylborane and an alkenyl halide in the presence of a base.
- Miyaura, Norio,Suginome, Hiroshi,Suzuki, Akira
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p. 1527 - 1530
(2007/10/02)
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- NEW STEREOSPECIFIC SYNTHESES OF PHEROMONE BOMBYKOL AND ITS THREE GEOMETRICAL ISOMERS
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New stereospecific syntheses of the pheromone bombykol and its three geometrical isomers are achieved by palladium-catalyzed cross-coupling reaction between an appropriate alkenylborane and an alkenyl halide in the presence of a base.
- Miyaura, Norio,Suginome, Hiroshi,Suzuki, Akira
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p. 3271 - 3278
(2007/10/02)
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- New Myocardial Imaging Agents: Stabilization of Radioiodine as a Terminal Vinyl Iodide Moiety on Tellurium Fatty Acids
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To determine the myocardial uptake and retention properties of radioiodinated tellurium fatty acids, we prepared two new tellurium fatty acids in which iodine-125 has been chemically stabilized by attachment as a trans-vinyl iodide (I-CH=CH-R-Te-R'-COOH)
- Knapp, F. F.,Goodman, M. M.,Callahan, A. P.,Ferren, L. A.,Kabalka, G. W.,Sastry, K. A. R.
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p. 1293 - 1300
(2007/10/02)
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- Recherches sur la synthese totale des alcaloides appatrenant a la serie de la carpaine et de la cassine. VII. Synthese totale de la (+/-) cassine
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11-Bromoundecan-2-one 6 was prepared in four steps from the commercially available undec-10-en-1-ol 3, and was used to alkylate ethyl 7-methyl-3-oxooct-6-enoate 9.The resulting intermediate was hydrolysed and decarboxylated to give the diketoolefin 11.Ozonolysis of the latter yielded the diketoaldehyde 16, wich was subjected next to condensation with nitroethane in alkaline conditions, followed by catalytic hydrogenation and cyclisation to give a ca. 50/50 mixture of 3-r-hydroxy-6-c (11-oxododecyl)-2-c-methylpiperidine and (+/-)3-epi-cassine. Another route to the key intemediate 11 was also studied, in wich 1,8-dibromooctane 13 was used to alkylate the enolates of ethyl acetoacetate and ethyl 7-methyl-3-oxooct-6-enoate, giving presumably of the olefinic diketodiester 15.Hydrolysis and decarboxylation of the crude reaction product, using aqueous baryum hydroxide, gave the desired compound 11 in an overall yield of 17 percent with respect to 1,8-dibromooctane 13.
- Brown, Eric,Bonte, Alain
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p. 281 - 287
(2007/10/02)
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