- Asymmetric total synthesis of (+)-exo-brevicomin based on enantioconvergent biocatalytic hydrolysis of an alkene-functionalized 2,3-disubstituted epoxide
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A short total asymmetric synthesis of (+)-exo- and (-)-endo-brevicomin ((+)-exo-3 and (-)-endo-3), which are components of the attracting pheromone system of several bark-beetle species belonging to the genera Dendroctonus and Dryocoetes, was accomplished via a chemoenzymatic protocol. The key step consisted of biocatalytic hydrolysis by bacterial epoxide hydrolases of cis-configured 2,3-disubstituted oxiranes bearing olefinic side chains. This reaction proceeded in an enantioconvergent fashion, by affording a single enantiomeric vic-diol from the rac-epoxide in up to 92% ee and 83% isolated yield.
- Mayer, Sandra F.,Mang, Harald,Steinreiber, Andreas,Saf, Robert,Faber, Kurt
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Read Online
- Thioether-Directed NiH-Catalyzed Remote γ-C(sp3)-H Hydroamidation of Alkenes by 1,4,2-Dioxazol-5-ones
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A NiH-catalyzed thioether-directed cyclometalation strategy is developed to enable remote methylene C-H bond amidation of unactivated alkenes. Due to the preference for five-membered nickelacycle formation, the chain-walking isomerization initiated by the NiH insertion to an alkene can be terminated at the γ-methylene site remote from the alkene moiety. By employing 2,9-dibutyl-1,10-phenanthroline as the ligand and dioxazolones as the reagent, the amidation occurs at the γ-C(sp3)-H bonds to afford the amide products in up to 90% yield (>40 examples) with remarkable regioselectivity (up to 24:1 rr).
- Chen, Qishu,Du, Bingnan,Ouyang, Yuxin,Yu, Wing-Yiu
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supporting information
p. 14962 - 14968
(2021/09/29)
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- Rapid Access to Highly Functionalized Alkyl Boronates by NiH-Catalyzed Remote Hydroarylation of Boron-Containing Alkenes
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The direct and selective functionalization of relatively simple and readily accessible precursors to produce highly functionalized alkyl boronates is a synthetically useful process. Herein we report a NiH-catalyzed remote hydroarylation process that can, through a synergistic combination of chain walking and subsequent cross-coupling, introduce an aryl group at the adjacent carbon atom of alkyl boronates under mild conditions. By means of a preliminary experiment with moderate enantioselectivity, it was shown that an asymmetric version could also be realized.
- Zhang, Yao,Han, Bo,Zhu, Shaolin
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supporting information
p. 13860 - 13864
(2019/08/08)
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- TASTE MODULATING ALDEHYDES
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Aldehydes of formula (I) (X represents an alkyl or alkenyl group having up to 9 carbon atoms) for use in taste modulation and/or flavor compositions are provided. Specifically, the compounds of the presently disclosed subject matter provide effective and unexpected taste modulating properties. The taste modulation and/or flavor compositions can be incorporated into various consumer end products in particular in combination with high intensity sweeteners.
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Page/Page column 29-30
(2018/03/28)
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- Synthesis of Diketones, Ketoesters, and Tetraketones by Electrochemical Oxidative Decarboxylation of Malonic Acid Derivatives: Application to the Synthesis of cis-Jasmone
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Disubstituted malonic acid derivatives are smoothly converted into diketones and ketoesters in good to excellent yield (68% to 91%) under electrochemical conditions. The scope can be extended to transform trisubstituted bis-malonic acids into tetraketones in 77% to 86% yield. The new method was applied to the total synthesis of cis-jasmone.
- Ma, Xiaofeng,Dewez, Damien F.,Du, Le,Luo, Xiya,Markó, István E.,Lam, Kevin
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- Synthesis of Diketones, Ketoesters, and Tetraketones by Electrochemical Oxidative Decarboxylation of Malonic Acid Derivatives: Application to the Synthesis of cis-Jasmone
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Disubstituted malonic acid derivatives are smoothly converted into diketones and ketoesters in good to excellent yield (68% to 91%) under electrochemical conditions. The scope can be extended to transform trisubstituted bis-malonic acids into tetraketones in 77% to 86% yield. The new method was applied to the total synthesis of cis-jasmone.
- Ma, Xiaofeng,Du, Le,Luo, Xiya,Markó, István E.,Dewez, Damien F.,Lam, Kevin
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p. 12044 - 12055
(2019/03/01)
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- Messenger RNA for the delivery composition and method (by machine translation)
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The present invention provides compositions comprising the lipid particles of encapsulated in mRNA molecular composition. Said composite particle comprising a cationic lipid, a non-cationic lipid and encapsulated in the lipid particles of the mRNA molecules in the lipid particle. The composition (for example) is used for the introduction of human subject suffering from a mRNA molecule, they are subject in said translation in order to produce the used to improve one or more of the symptoms of the disease polypeptide. The invention also provides for the preparation of said composition of the present invention a cationic lipid. (by machine translation)
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Paragraph 0469; 0475; 0476; 0477
(2016/10/09)
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- COMPOSITIONS AND METHODS FOR DELIVERING MESSENGER RNA
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The present invention provides compositions comprising mRNA molecules encapsulated within lipid particles. The lipid particles comprise a cationic lipid, a non-cationic lipid, and an mRNA molecule that is encapsulated within the lipid particle. The compositions are useful, for example, to introduce the mRNA molecules into a human subject where they are translated to produce a polypeptide that functions to ameliorate one or more symptoms of a disease. The invention also provides cationic lipids that are useful for preparing the compositions of the invention.
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Paragraph 0306
(2016/06/28)
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- COMPOSITIONS AND METHODS FOR DELIVERING MESSENGER RNA
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The present invention provides compositions comprising mRNA molecules encapsulated within lipid particles. The lipid particles comprise a cationic lipid, a non-cationic lipid, and an mRNA molecule that is encapsulated within the lipid particle. The compositions are useful, for example, to introduce the mRNA molecules into a human subject where they are translated to produce a polypeptide that functions to ameliorate one or more symptoms of a disease. The invention also provides cationic lipids that are useful for preparing the compositions of the invention.
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Page/Page column 81
(2015/10/05)
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- Organic Compounds
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Disclosed are compounds having the ability to inhibit cytochrome P450 2A6, 2A13, and/or 2B6 and tobacco products comprising them. Also disclosed are pharmaceutical compositions comprising them.
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Page/Page column 10
(2010/05/13)
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- Enzyme-triggered enantioconvergent transformation of haloalkyl epoxides
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Biocatalytic hydrolysis of 2,3-disubstituted rac-cis- and rac-trans-haloalkyl epoxides 1a-8a using the epoxide hydrolase activity of whole bacterial cells furnished the corresponding vicinal diols 1b-8b as intermediates; these (spontaneously) underwent ring closure to yield cyclic products 1c-6c through an enzyme-triggered cascade reaction. In particular, cis-configured substrates (1a, 3a, 5a, 7a) were transformed in an enantioconvergent fashion, which resulted in the formation of single stereoisomeric products in 100% des and up to 92% ees from the racemates.
- Mayer, Sandra F.,Steinreiber, Andreas,Orru, Romano V. A.,Faber, Kurt
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p. 4537 - 4542
(2007/10/03)
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- Penicillin acylase-mediated synthesis of 2-acetyl-1-pyrroline and of 2-propionyl-1-pyrroline, key roast-smelling odorants in food. Inclusion complexes with i-cyclodextrin and their NMR and MS characterization
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The synthesis of the strong natural roast odorants 1 and 2 is achieved from the C-6 isomeric alcohols 16 and 21 via the acetylenic C-6 and C-7 amines 8 and 9. Key step in the process is the hydrolysis of the W-phenylacetamides 12 and 13 by means of immobilized penicillin acylase, which affords the l-amino-4,5-diketones 14 and 15, spontaneously ring closing to 1 and 2. These latter compounds form inclusion complexes with/?-cyclodextrin, as demonstrated by NMR measurements in deuterated water and FAB-MS spectra.
- Favino, Tito Fabrizio,Fronza, Giovanni,Fuganti, Claudio,Fuganti, Daniela,Grasselli, Piero,Mele, Andrea
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p. 8975 - 8979
(2007/10/03)
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- Pheromone specificity in Eriocrania semipurpurella (Stephens) and E. sangii (Wood) (lepidoptera: eriocraniidae) based on chirality of semiochemicals
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1966 Plenum Publishing Corporation. The fifth abdominal segment of female Eriocrania semipurpurella (Stephens) and E, sangii (Wood) contains a pair of exocrine glands. Hexane extracts of this segment were prepared from both species and analyzed by gas chromatography with simultaneous flame ionization and electroantennographic detection (EAD). For both species, the EAD active peaks were identified as nonan-2-one, (Z)-6-nonen-2-one, and (Z)-6-nonen-2-ol by means of mass spectrometry and comparison of retention indices with those of synthetic standards. Enantiomeric separation of chiral alcohols from the female extracts was achieved by gas Chromatographic analysis on a cyclodextrin column. In E. semipurpurella, a mixture of (2S,6Z)-nonen-2-ol and (2R,6Z)-nonen-2-ol (2:1) was found, whereas in E. sangii (2S,6Z)-nonen-2-ol was the predominant enantiomer and only traces of the R enantiomer were indicated by the antennal response. In field tests, a blend of the three compounds was not attractive to conspecific males. A subtractive assay showed that the alcohol in various enantiomeric mixtures was the only attractive compound, whereas addition of (Z)-6-nonen-2-one to the alcohol completely inhibited the attraction of both species. A trapping experiment including a wide range of ratios between the R and 5 enantiomers showed that baits containing 95-100% of the S enantiomer were attractive to male E. sangii, whereas males of E, semipurpurella were attracted to all tested ratios of the enantiomers. However, the response profiles of male E. semipurpurella differed between populations from southern Sweden, south Finland, and the Kola Peninsula in Russia. In south Sweden males were maximally attracted to a racemic mixture of the alcohols. At the Kola Peninsula E. semipurpurella was attracted to baits containing 95-100% of the A enantiomer. In south Finland all tested ratios between 0 and 100% R enantiomer trapped E. semipurpurella, but the trap catches appeared to be bimodally distributed with peaks around 15 and 70% R enantiomer. The trapping results suggest the existence of pheromone races or sibling species among the specimens identified as E. semipurpurella.
- Kozlov, Michail V.,Zhu, Junwei,Philipp, Peter,Francke, Wittko,Zvereva, Elena L.,Hansson, Bill S.,Loefstedt, Christer
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p. 431 - 454
(2007/10/03)
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- A facile entry to secondary cyclopropylcarbinols: Further developments in the stereospecific synthesis of (E)-homoallylic bromides
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Cyclopropanecarboxaldehyde has been used in an improved synthesis of secondary cyclopropylcarbinols, thus allowing for further developments in the stereospecific ring opening leading to (E)-homoallylic bromides.
- Ferreri,Ambrosone,Chatgilialoglu
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p. 3351 - 3356
(2007/10/03)
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- STEREOSELECTIVE SYNTHESIS OF HYDROXY OCTADECATRIENOIC ACIDS. THE SELF DEFENSIVE SUBSTANCES IN RICE PLANT
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Convenient synthesis of 16-hydroxy-9Z,12Z,14E-octadecatrienoic acid (1) and 9-hydroxy-10E,12Z,15Z-octadecatrienoic acid (2) the self defensive substances in rice plant against rice blast disease are described.
- Rao, A. V. Rama,Reddy, E. Rajarathnam
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p. 2279 - 2282
(2007/10/02)
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- Identification and Synthesis of New γ-Lactones from Tuberose Absolute (Polianthes tuberosa)
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Six unsaturated γ-lactones, (Z)-5-octen-4-olide (1), (Z)-5-decen-4-olide (2), (Z)-6-nonen-4-olide (3), (Z)-6-dodecen-4-olide (4), (Z,Z)-6,9-dodecadien-4-olide (5), and tuberolide (6) have been identified for the first time in tuberose absolute (from Polianthes tuberosa L.).All structures were corroborated by synthesis and all, except 3 and 4, are new.An improved method for the stereoselective synthesis of (+/-)-cis-bicyclo-non-3-en-7-one (23) by an AlCl3-catalyzed Diels-Alder reaction is reported.
- Maurer, Bruno,Hauser, Arnold
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p. 462 - 476
(2007/10/02)
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