- INSECT PHEROMONES AND THEIR ANALOGUES XXX. SYNTHESIS OF OCTA-2E,6E-DIENE-1,8-DIOL DIISOVALERATE - THE SEX PHEROMONE OF Agriotes tauricus
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The synthesis has been effected of octa-2E,6E-diene-1,8-diol diisovalerate - the sex pheromone of the Crimean click beetle Agriotes tauricus - by the carboxymethylenation of the readilly available 6-methylhept-5-en-2-one, the allyl oxidation of a terminal methyl group, reduction of the ester fraction, and interaction of the diol so obtained with isovaleryl chloride.The required pheromone can also bee obtained from available cyclic oligomers of isoprene.
- Odinokov, V. N.,Kukovinets, O. S.,Sakharova, N. I.,Tolstikov, G. A.
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- Iridium-Catalyzed Asymmetric Isomerization of Primary Allylic Alcohols Using MaxPHOX Ligands: Experimental and Theoretical Study
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The asymmetric isomerization of primary allylic alcohols to chiral aldehydes using iridium-catalysts bearing P,N-MaxPHOX ligands has been studied. These catalysts can be fine-tuned as they present three different stereogenic centers to modulate both the reactivity and enantioselectivity of a family of different substrates. The experimental part is supported by a DFT study of the reaction mechanism, which provides new insights into the key steps of this transformation.
- Cabré, Albert,Gar?on, Martí,Gallen, Albert,Grisoni, Lorenzo,Grabulosa, Arnald,Verdaguer, Xavier,Riera, Antoni
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p. 4112 - 4120
(2020/07/04)
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- Transition-Metal-Free Formylation of Allylzinc Reagents Leading to α-Quaternary Aldehydes
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The first example of formylation of allylzinc reagents using S-phenyl thioformate is presented. The reaction proceeded under mild conditions without any transition-metal catalyst, forming quaternary carbon centers with reactive functionalities, such as formyl and vinyl groups. Moreover, Barbier-type formylation of an allylic bromide with a sterically demanding thioformate was achieved. As a preliminary result, asymmetric formylation was conducted using a menthol-derived chiral thioformate.
- Haraguchi, Ryosuke,Kusakabe, Akinori,Mizutani, Nakaba,Fukuzawa, Shin-Ichi
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supporting information
p. 1613 - 1616
(2018/03/23)
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- Agent having neurotrophic factor-like activity
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The present invention provides a pharmaceutical agent having high safety and a neurotrophic factor-like activity, which contains, as an active ingredient, any one compound included in fatty acids each having 8 carbon atoms (C8) or having 10 carbon atoms (C10) to 12 carbon atoms (C12) or fatty acid esters thereof, such as 3,7-dimethyloctanoic acid ethyl ester, geranicacidethyl ester, and the like, eachof whichhas 8 carbonatoms (C8), decanoic acid methyl ester, trans-2-decenoic acid, trans-2-decenoic acid methyl ester, trans-2-decenoic acid ethyl ester, trans-2-decenoic acid-2-decenyl ester, trans-2-decenoic acid cyclohexyl ester, trans-2-decenoic acid isopropyl ester, trans-3-decenoic acid methyl ester, trans-9-decenoic acid methyl ester, and the like, each of which has 10 carbon atoms (C10), trans-10-undecenoic acid methyl ester, trans-10-undecenoic acid ethyl ester, and the like, each of which has 11 carbon atoms (C11), and dodecanoic acid, and the like, each of which has 12 carbon atoms (C12), or salts thereof or prodrugs thereof.
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Paragraph 0061-0062
(2016/01/25)
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- Conformational Analysis, Thermal Rearrangement, and EI-MS Fragmentation Mechanism of (1(10)E,4E,6S,7R)-Germacradien-6-ol by 13C-Labeling Experiments
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An uncharacterized terpene cyclase from Streptomyces pratensis was identified as (+)-(1(10)E,4E,6S,7R)-germacradien-6-ol synthase. The enzyme product exists as two interconvertible conformers, resulting in complex NMR spectra. For the complete assignment of NMR data, all fifteen (13C1)FPP isotopomers (FPP=farnesyl diphosphate) and (13C15)FPP were synthesized and enzymatically converted. The products were analyzed using various NMR techniques, including 13C, 13C COSY experiments. The (13C)FPP isotopomers were also used to investigate the thermal rearrangement and EI fragmentation of the enzyme product. All 15 isotopomers of (13C1)- and fully labeled (13C15)farnesyl diphosphate were synthesized and converted to the title compound by a newly characterized bacterial terpene cyclase from Streptomyces pratensis. The enzyme products were used for structure elucidation of the sesquiterpene alcohol, full assignment of NMR data and a conformational analysis, and investigation of its Cope rearrangement and of its EI-MS fragmentation mechanism.
- Rabe, Patrick,Barra, Lena,Rinkel, Jan,Riclea, Ramona,Citron, Christian A.,Klapschinski, Tim A.,Janusko, Aron,Dickschat, Jeroen S.
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supporting information
p. 13448 - 13451
(2015/11/09)
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- CuI/Pd0 cooperative dual catalysis: Tunable stereoselective construction of tetra-substituted alkenes
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This paper describes a tunable and stereoselective dual catalytic system that uses copper and palladium reagents. This cooperative silylcupration and palladium-catalyzed allylation readily affords trisubstituted alkenylsilanes. Fine-tuning the reaction conditions allows selective access to one stereoisomer over the other. This new methodology tolerates different substituents on both coupling partners with high levels of stereoselectivity. The one-pot reaction involving a CuI/Pd0 cooperative dual catalyst directly addresses the need to develop more time-efficient and less-wasteful synthetic pathways.
- Vercruysse, Sebastien,Cornelissen, Loic,Nahra, Fady,Collard, Laurent,Riant, Olivier
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supporting information
p. 1834 - 1838
(2014/03/21)
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- Synthesis of farnesol isomers via a modified wittig procedure
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(Chemical Equation Presented) The four olefin stereoisomers of farnesol have been synthesized from readily available nerylacetone or commercial geranylacetone. A new variation on the use of β-oxido ylides favored the (2Z)-stereoisomers, whereas the (2E)-isomers were obtained through a classical Horner-Wadsworth-Emmons condensation with triethyl phosphonoacetate and reduction of the resulting ester.
- Yu, Jose S.,Kleckley, Troy S.,Wiemer, David F.
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p. 4803 - 4806
(2007/10/03)
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- Two-carbons homologation of methyl ketones examplified for the synthesis of citral from 6-methyl-5-hepten-2-one
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New facile syntheses of 3,7-dimethyl-octadien-2,6-al (citral) from homologation of 6-methyl-5-hepten-2-one are reported.
- Valla, Alain,Cartier, Dominique,Laurent, Alain,Valla, Benoist,Labia, Roger,Potier, Pierre
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p. 1195 - 1201
(2007/10/03)
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- Approaches to selective isoprenologation via reactions of (η3-allyl)Fe(CO)4+ with allyl nucleophiles
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The reactions of substituted (η3-allyl)Fe(CO)4BF4 complexes 1 with various allyl-metals and dienolate derivatives have been investigated in search of a method for regio- and stereocontrolled allyl-allyl coupling.All three classes of allyl derivatives react with 1 in moderate to good yield with variable regioselectivity; the silyl derivatives 2 generally provide good regioselectivity for attack at the less substituted terminus of unsymmetrical derivatives of 1 but deprotonation of the 1,1-dimethylallyl complex 1e prevents efficient isoprenylation.Although deprotonation of 1e also dominates with the siloxydienes, the lithium dienolates couple efficiently with 1; however, reaction at the α position of the dienolate dominates.
- Li, Zhong,Nicholas, Kenneth M.
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p. 105 - 112
(2007/10/02)
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- MOLIBDENUM HEXACARBONYL AS A THIOPHILIC METAL REAGENT: DESULFENYLATIVE ALLYLATION USING ALLYLIC SULFIDES
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Molybdenum hexacarbonyl is a useful reagent for desulfenylative allylation of carbon nucleophiles with allylic sulfides.
- Masuyama, Yoshiro,Yamada, Kohji,Kurusu, Yasuhiko
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p. 443 - 444
(2007/10/02)
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- Functionalization of terminal trisubstituted alkenes and derivatives thereof
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The invention relates to a process for preparing compounds having the general structure: STR1 wherein R is hydrogen or an acyclic or alicyclic fragment containing between one and about ten carbon atoms, and R1 is hydrogen or an alkyl containing between one and about four carbon atoms or an aryl group.
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- ALDOL REACTIONS, CONJUGATE ADDITIONS, AND ALKYLATION REACTIONS OF O-SILYLATED KETENE ACETALS UNDER NEUTRAL CONDITIONS
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Aldol reactions, conjugate additions, and alkylation reactions of O-silylated ketene acetals take place under neutral conditions by using a high pressure technique.
- Yamamoto, Yoshinori,Maruyama, Kazuhiro,Matsumoto, Kiyoshi
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p. 1075 - 1078
(2007/10/02)
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- Regioselective Head-to-tail Coupling of Allylic Trialkylstannanes with Allylic Halides under High Pressure
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Allylic trialkylstannanes (1) regioselectively react with allylic halides (2) at room temperature under high pressure (10 kbar) to give head-to-tail coupling products (3) in high yields.
- Yamamoto, Yoshinori,Maruyama, Kazuhiro,Matsumoto, Kiyoshi
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p. 548 - 549
(2007/10/02)
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- A SIMPLE SYNTHESIS OF α,β-UNSATURATED CARBONYL COMPOUNDS BY TRAPPING THE MICHAEL ADDITION-ENOLATE ANION WITH METHANESULFINYL CHLORIDE
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Trapping of an enolate anion, formed by the Michael addition, with methanesulfinyl chloride and subsequent desulfinylation is found to be a useful method for the synthesis of various α,β-unsaturated carbonyl compounds.Synthetic utility of this method is demonstrated in the synthesis of geraniol, nerol, farnesol, and dihydrojasmone.
- Fujisawa, Tamotsu,Noda, Atsunari,Kawara, Tatsuo,Sato, Toshio
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p. 1159 - 1160
(2007/10/02)
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