- OLIGONUCLEOTIDE COMPOSITIONS AND METHODS THEREOF
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The present disclosure provides modified oligonucleotides and compositions and methods thereof. In some embodiments, provided technologies comprise modified sugars and/or modified internucleotidic linkages. In some embodiments, the present disclosure provides technologies for preparing modified oligonucleotides. In some embodiments, the present disclosure provides chirally controlled oligonucleotide compositions and methods for their preparation and uses.
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Paragraph 00815; 00816
(2021/11/26)
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- Beyond Amphiphilic Balance: Changing Subunit Stereochemistry Alters the Pore-Forming Activity of Nylon-3 Polymers
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Amphiphilic nylon-3 polymers have been reported to mimic the biological activities of natural antimicrobial peptides, with high potency against bacteria and minimal toxicity toward eukaryotic cells. Amphiphilic balance, determined by the proportions of hydrophilic and lipophilic subunits, is considered one of the most important features for achieving this activity profile for nylon-3 polymers and many other antimicrobial polymers. Insufficient hydrophobicity often correlates with weak activities against bacteria, whereas excessive hydrophobicity correlates with high toxicity toward eukaryotic cells. To ask whether factors beyond amphiphilic balance influence polymer activities, we synthesized and evaluated new nylon-3 polymers with two stereoisomeric subunits, each bearing an ethyl side chain and an aminomethyl side chain. Subunits that differ only in stereochemistry are predicted to contribute equally to amphiphilic balance, but we observed that the stereochemical difference correlates with significant changes in biological activity profile. Antibacterial activities were not strongly affected by subunit stereochemistry, but the ability to disrupt eukaryotic cell membranes varied considerably. Experiments with planar lipid bilayers and synthetic liposomes suggested that eukaryotic membrane disruption results from polymer-mediated formation of large pores. Collectively, our results suggest that factors other than amphiphilic balance influence the membrane activity profile of synthetic polymers. Subunits that differ in stereochemistry are likely to have distinct conformational propensities, which could potentially lead to differences in the average shapes of polymer chains, even when the subunits are heterochiral. These findings highlight a dimension of polymer design that should be considered more broadly in efforts to improve specificity and efficacy of antimicrobial polymers.
- Liu, Lei,Courtney, Kevin C.,Huth, Sean W.,Rank, Leslie A.,Weisblum, Bernard,Chapman, Edwin R.,Gellman, Samuel H.
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supporting information
p. 3219 - 3230
(2021/03/08)
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- Visible Light-Mediated Photochemical Reactions of 2-(2′-Alkenyloxy)cycloalk-2-enones
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The title compounds were prepared, and their reactivity was studied upon sensitized irradiation at λ = 420 nm. Thioxanthen-9-one was employed as the sensitizer at a loading of 10 mol % in small-scale reactions and of 2.5 mol % on a larger scale. Cyclohex-
- Gra?l, Raphaela,Jandl, Christian,Bach, Thorsten
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p. 11426 - 11439
(2020/10/12)
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- METHODS FOR PREPARATION OF JASMONATE COMPOUNDS
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This invention relates to methods for preparation of jasmonate compounds via a salt of jasmonic acid.
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Paragraph 045
(2019/07/20)
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- Electrophilic rearrangements of chiral amides: A traceless asymmetric α-allylation
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A one-pot protocol for the asymmetric α-allylation reaction is reported relying on a key efficient asymmetric Claisen rearrangement, triggered by electrophilic activation of chiral pseudoephedrine amides. Subsequent reduction or hydrolysis of the resulting iminium ions provides highly enantioenriched α-allylic aldehydes or carboxylic acids in a traceless manner. Compared to traditional alternatives which make use of strongly basic conditions, the work presented herein displays unprecedented functional group tolerance.
- Peng, Bo,Geerdink, Danny,Maulide, Nuno
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supporting information
p. 14968 - 14971
(2013/11/06)
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- A highly reusable rhodium catalyst-organic framework for the intramolecular cycloisomerization of 1,6-enynes
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The intramolecular cycloisomerization of 1,6-enynes in 95-99% ee is reported using an immobilized Rh catalyst-organic framework synthesized from alternating ring-opening metathesis polymerization (altROMP) assembly. The framework was reused up to seven times, and it was used in high turnover number (TON) batch reactions. The catalyst provided the highest TONs to date (up to 890) for the cycloisomerizations, with catalyst loadings ranging from 0.2 to 0.06 mol %.
- Corkum, Elizabeth G.,Hass, Michael J.,Sullivan, Andrew D.,Bergens, Steven H.
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supporting information; experimental part
p. 3522 - 3525
(2011/09/16)
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- Protective group-free syntheses of (±)-frontalin, (±)-endo-brevicomin, (±)-exo-brevicomin, and (±)-3,4- dehydro-exo-brevicomin: Racemic pheromones with a 6,8-dioxabicyclo[3.2.1]octane ring
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Protective group-free syntheses of four racemic pheromones with a 6,8-dioxabicyclo[3.2.1]octane ring were achieved in five or six steps from commercially available (±)-3-butyn-2-ol (6) and 2-alkenyl halides or 2-alken-1-ol by employing Lewis acid-catalyzed acetalization of δ, ε-epoxy ketones as the key reaction. (±)- Frontalin (1) was prepared in a 25% overall yield in five steps from methallyl chloride (5a), (±)-endo-brevicomin (2) was prepared in a 23% overall yield in five steps from (E)-2-pentenyl bromide (5b), and (±)-exo-brevicomin (3) and (±)-3,4-dehydro-exo-brevicomin (4) were both prepared in a 4%overall yield in six steps based on (Z)-2-penten-1-ol (12).
- Mori, Kenji
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body text
p. 976 - 981
(2012/01/05)
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- Unexpected electrophilic rearrangements of amides: A stereoselective entry to challenging substituted lactones
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"Chemical Equation Presented" Surprise, surprise! An unexpected skeletal rearrangement was developed into a chemo- and stereoselective synthesis of aallyl and allenyl lactones with challenging substitution patterns (see scheme; EWC = electron-withdrawing group). The generality, unique features, and synthetic potential of this reaction were probed and a mechanism was proposed.
- Madelaine, Claire,Valerio, Viviana,Maulide, Nuno
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supporting information; experimental part
p. 1583 - 1586
(2010/06/15)
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- Microwave assisted synthesis of unsaturated jasmone heterocyclic analogues as new fragrant substances
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Taking the rising interest in jasmone structure based fragrant compounds into account it has been decided to take up an attempt to synthesize the new heterocyclic derivatives of this 2,3-disubstituted cyclopentenone, which could be characterized by the ability of interaction with the same receptors with which jasmone affects. Obtained structures of unsaturated heterocyclic derivatives are based on pyrrolidinone, oxazolidinone, pyrazolidinone, pyrazolone and thiazolidinone systems with 2-double or 2-triple unsaturated five-carbon side chain. The rapid, highly yielding and ecofriendly microwave assisted organic syntheses (MAOS) have been used to obtain compounds mentioned above. Odor evaluation and relationships between their structure and osmic properties for all synthesized fragrant compounds have been studied. It has been shown that the majority of the obtained compounds have exhibited interesting, very intensive and fixative fragrant properties.
- Pawelczyk, Anna,Zaprutko, Lucjusz
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body text
p. 3032 - 3039
(2009/10/02)
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- Synthesis and self-photooxygenation of alkenyl-linked [60]fullerene derivatives. A regioselective ene reaction
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(equation presented) Alkenyl-linked C60 derivatives undergo self-photooxygenation regioselectively, by the preferential abstraction of allylic hydrogens on the fullerene side of the double bond.
- Chronakis, Nikos,Vougioukalakis, Georgios C.,Orfanopoulos, Michael
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p. 945 - 948
(2007/10/03)
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- Synthesis of a pheromone of Boarmia selenaria via a Sila-Cope elimination. Stereochemical implications
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The use of a Sila-Cope elimination afforded a Z,Z,Z trienamine derivative, direct synthetic precursor of (3Z,6Z,9Z)-3,6,9-nonadecatriene 1, one of the pheromone components of Boarmia selenaria. X-ray analysis of the tetrahydropyridinium salt 13 leading to
- Langlois,Konopski,Bac,Chiaroni,Riche
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p. 1865 - 1868
(2007/10/02)
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- Exo- and Endohormones. X. A Novel Route to an Isomer Mixture of 7,9-Dodecadien-1-yl Acetate Utilizable in Field Attraction of Lobesia botrana Males
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Wittig condensation of (Z)-2-pentenylidene triphenylphosphorane (14) and 7-tert.-butoxy-heptanal (13) under conditions of phase transfer catalysis and subsequent conversion into the corresponding acetate afforded a mixture of 28percent 7(E),9(Z)-dodecadien-1-yl acetate, the sex pheromone of Lobesia botrana, along with the other geometrical isomers and 30percent unidentified by-products.The synthons 14 and 13 were prepared starting with (Z)-2-butene-1,4-diol (1) and hexane-1,6-diol (9), respectively.
- Daradics, L.,Oprean, I.,Hodosan, F.
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p. 277 - 282
(2007/10/02)
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- Synthesis of Dienic Pheromones of Codling Moth and Grape Vine Moth
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The synthesis of pheromones 8E,10E-dodecadien-1-ol (I) and 7E,9Z-dodecadien-1-yl acetate (II) via sulphone intermediates has been accomplished.The α-anions of the sulphones (2) and (10) on reaction with the aldehydes (5) and (11) followed by acetylation of the resulting products in situ afford the β-acetoxysulphones (6) and (12) respectively.Reductive elimination of 6 and 12 with Na/Hg provide the dienic compounds, which on depyranylation and acetolysis yield I and II respectively.
- Kulkarni, S. M.,Mamdapur, V. R.,Chadha, M. S.
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p. 1208 - 1210
(2007/10/02)
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- 211. Michael Addition of Lithio-α-(methyldiphenylsilyl)acetate to Cyclopentenone: A Direct Synthesis of (+/-)-Methyl Jasmonate
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Aprotic 1,4-addition of a lithiated α-(methyldiphenylsilyl)acetate to cyclopentenone and in situ enolate alkylation provides a direct synthesis of (+/-)-methyl jasmonate (Scheme 3).
- Oppolzer, Wolfgang,Guo, Modao,Baetting, Kurt
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p. 2140 - 2144
(2007/10/02)
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