- MODIFIED AMINE LIPIDS
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The disclosure provides ionizable amine lipids and salts thereof (e.g., pharmaceutically acceptable salts thereof) useful for the delivery of biologically active agents, for example delivering biologically active agents to cells to prepare engineered cells. The ionizable amine lipids disclosed herein are useful as ionizable lipids in the formulation of lipid nanoparticle-based compositions.
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Page/Page column 251-253; 255-256
(2020/07/04)
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- Diastereo- and Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols in Two Steps from Terminal Alkynes
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We report the highly diastereo- and enantioselective preparation of (E)-δ-boryl-substituted anti-homoallylic alcohols in two steps from terminal alkynes. This method consists of a cobalt(II)-catalyzed 1,1-diboration reaction of terminal alkynes with B2pin2 and a palladium(I)-mediated asymmetric allylation reaction of the resulting 1,1-di(boryl)alk-1-enes with aldehydes in the presence of a chiral phosphoric acid. Propyne, which is produced as the byproduct during petroleum refining, could be used as the starting material to construct homoallylic alcohols that are otherwise difficult to synthesize with high stereocontrol.
- Miura, Tomoya,Oku, Naoki,Murakami, Masahiro
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supporting information
p. 14620 - 14624
(2019/09/06)
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- Chiral Surfactant-Type Catalyst: Enantioselective Reduction of Long-Chain Aliphatic Ketoesters in Water
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A series of amphiphilic ligands were designed and synthesized. The rhodium complexes with the ligands were applied to the asymmetric transfer hydrogenation of broad range of long-chained aliphatic ketoesters in neat water. Quantitative conversion and excellent enantioselectivity (up to 99% ee) was observed for α-, β-, γ-, δ- and ε-ketoesters as well as for α- and β-acyloxyketone using chiral surfactant-type catalyst 2. The CH/π interaction and the strong hydrophobic interaction of long aliphatic chains between the catalyst and the substrate in the metallomicelle core played a key role in the catalytic transition state. Synergistic effects between the metal-catalyzed site and the hydrophobic microenvironment of the core in the micelle contributed to high stereoselectivity. (Chemical Equation Presented).
- Lin, Zechao,Li, Jiahong,Huang, Qingfei,Huang, Qiuya,Wang, Qiwei,Tang, Lei,Gong, Deying,Yang, Jun,Zhu, Jin,Deng, Jingen
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p. 4419 - 4429
(2015/05/13)
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- Enantioselective transesterification of (±)1phenylundecan-3-ol catalyzed by the lipase from Burkholderia cepacia
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Enantiomerically enriched (R) and (S)-1-phenylundecan-3-ols were obtained by kinetic resolution of the racemate with vinyl acetate in ButOMe at 20 °C using the lipase from Burkhold eria cepacia. The absolute configuration of the enantiomers was
- Vlasyuk,Voblikova,Gamalevich,Serebryakov
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p. 2041 - 2045
(2014/07/07)
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- Synthesis of optically active heterocyclic compounds via deracemization of 1,2-diol monotosylate derivatives bearing a long aliphatic chain by a combination of enzymatic hydrolysis with Mitsunobu inversion
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We have succeeded in accomplishing the deracemization of (±)-2-acetoxydecyl and (±)-acetoxy-6-benzyloxyhexyl tosylates, which have a long substituent, via an enzyme-mediated enantioselective hydrolysis with a Mitsunobu inversion using polymer-supported triphenylphosphine to afford the corresponding (S)-enantiomer. Enantiomerically pure (S)- and (R)-γ-dodecalactones, a fruit flavor, were synthesized from (S)-2-acetoxydecyl tosylate as the mutual starting material. The poisonous alkaloid (S)-coniine was also synthesized using enantiomerically pure allyl amine as the key intermediate derived from (S)-acetoxy-6-benzyloxyhexyl tosylate.
- Matsumoto, Kazutsugu,Usuda, Kazumasa,Okabe, Hirokazu,Hashimoto, Manabu,Shimada, Yasutaka
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p. 108 - 115
(2013/04/23)
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- Cyclodextrin-based ionic liquids as enantioselective stationary phases in gas chromatography
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New permethylated mono-6-deoxy-6-pyridin-1-ium and mono-6-deoxy-6-(1-vinyl- 1H-imidazol-3-ium)-α- and -β-cyclodextrin trifluoromethanesulfonate ionic liquids were synthesized from the corresponding permethylated mono-6-hydroxycyclodextrins in a one-pot reaction and solvent-free procedure. Regioselective transformation of native α- and β-cyclodextrins with the use of a bulky tert-butyldiphenylsilyl protecting group afforded the desired 6-monosubstituted permethylated cyclodextrin derivatives in moderate yields. The new ionic liquids were tested as stationary phases in capillary GC columns towards chiral discrimination in enantio-GC analysis of racemic mixtures. The permethylated 6-deoxy-6-pyridin-1-ium-α-cyclodextrin trifluoromethanesulfonate displayed good enantiomeric separations for some racemic esters and lactones, as well as epoxides. In particular, for both the racemic whiskey lactone and the high boiling point menthyl laurate, not successfully separated in a commercial cyclodextrin phase, the enantiomeric separations were achieved isothermally at 140 °C. In phase: Permethylated mono-6-hydroxy-α- and -β-cyclodextrins react with pyridine or 1-vinylimidazole in the presence of triflic anhydride in a solvent-free procedure to yield new roomerature ionic liquids (ILs). These ILs have been used as stationary phases in gas chromatography; enantiomeric separations are achieved (see figure for whiskey lactone) with permethylated mono-6-deoxy-6-(pyridin-1-ium)-α-cyclodextrin trifluoromethanesulfonate. Copyright
- Costa, Nuno,Matos, Sara,Da Silva, Marco D. R. Gomes,Pereira, M. Manuela A.
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p. 1466 - 1474
(2014/01/06)
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- Combination of novozym 435-catalyzed hydrolysis and mitsunobu reaction for production of (r)γ-lactones
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Chiral-lactones of both enantiomers were synthesized with more than 90% optical purities. The key step was Novozym 435-catalyzed hydrolysis of racemic N-benzyl-4-acetoxyalkylamides. Additionally, because (R)-γ-lactones are predominant in apricot, mango, peach, passion fruit, and strawberry, synthesis was attempted using only one enantiomer selectively. The (R)-enantimer was synthesized with more than 80% total yield and more than 90% optical purity by a combination of Novozym 435-catalyzed hydrolysis and the Mitsunobu reaction. Copyright
- Shimotori, Yasutaka,Miyakoshi, Tetsuo
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experimental part
p. 1607 - 1613
(2010/06/21)
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- Synthesis of (S)-γ- lactones with a combination of lipase-catalyzed resolution and mitsunobu reaction
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Six kinds of (S) - lactones [e.g., (S) - decalactone, (S) - undecalactone, and (S) - jasmolactone] were synthesized with 71-88% yields and 97% optical purities by combining lipase-catalyzed resolution with the Mitsunobu reaction. Copyright Taylor & Francis Group, LLC.
- Shimotori, Yasutaka,Miyakoshi, Tetsuo
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experimental part
p. 1570 - 1582
(2009/11/30)
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- Ligand effects in aluminium-catalyzed asymmetric Baeyer-Villiger reactions
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Asymmetric Baeyer-Villiger oxidations of racemic and prochiral cyclobutanones can be performed with chiral aluminium-based Lewis acids resulting in products with good enantioselectivities in high yields. By employing substituted BINOL derivatives as ligan
- Frison, Jean-Cédric,Palazzi, Chiara,Bolm, Carsten
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p. 6700 - 6706
(2007/10/03)
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- Lactone synthesis via biotransformations of γ-hydroxyamides
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An enzyme was expressed in E. coli from a cloned amidase gene. When characterized, it was more enantioselective than commercial amidases. Three pheromones were made. An enzyme was expressed in Escherichia coli from a cloned amidase gene. When characterized, it was more enantioselective than commercial amidases. Three pheromones were made using this biotransformation chemistry.
- Taylor, Stephen K.,Arnold, Carrie R.,Gerds, Aaron T.,Ide, Nathan D.,Law, Keri M.,Kling, Dale L.,Pridgeon, Matthew G.,Simons, Lloyd J.,Vyvyan, James R.,Yamaoka, Jennifer S.,Liao, Min-Ken,Goyne, Thomas E.
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p. 3819 - 3821
(2007/10/03)
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- Facile synthesis of optically active γ-lactones via lipase-catalyzed reaction of 4-substituted 4-hydroxybutyramides
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Lipase-catalyzed transesterification of racemic 4-substituted 4- hydroxybutyramides with succinic anhydride proceeded enantioselectively to afford (S)-succinic acid monoester and unreacted (R)-4-hydroxybutyramide derivative, which were separated easily by
- Matsumura, Yasufumi,Endo, Teruko,Chiba, Mitsuo,Fukawa, Hidemichi,Terao, Yoshiyasu
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p. 304 - 305
(2007/10/03)
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- Syntheses of rac- and optically active 2-alkyl-γ-butyrolactones and 2- alkyl-cyclobutanones
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γ-Butyrolactones have been produced in good yield from alkylidene cyclopropanes, as racemates or as an enantiomerically enriched mixture of stereoisomers (e.e.>60%) depending upon the method used. Optically active cyclobutanones which are intermediate in the process have been in some cases isolated. We show the limitations of a competitive method previously described and point out its weak step.
- Krief, Alain,Ronvaux, Alain,Tuch, Arounarith
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p. 6903 - 6908
(2007/10/03)
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- Synthesis of Optically Active Butenolides and γ-Lactones by the Sharpless Asymmetric Dihydroxylation of β,γ-Unsaturated Carboxylic Esters
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Keywords: asymmetric synthesis; butenolides; dihydroxylations; furanones; lactones
- Harcken, Christian,Brueckner, Reinhard
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p. 2750 - 2752
(2007/10/03)
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- Synthesis and absolute stereochemistry of Hagen's-Gland lactones in some parasitic wasps (Hymenoptera:Braconidae)
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Efficient syntheses and enantioselective gas chromatography have confirmed the structures and established the absolute stcreochemistry of some novel bicyclic lactones (tetrahydrofurofuranones) in species of parasitic wasps (Hymenoptera:Braconidae). The co-occurring γ-lactones, octan-4-olide and dodecan-4-olide, have the (R)-configuation.
- Paddon-Jones, Gregory C.,Moore, Christopher J.,Brecknell, Douglas J.,Koenig, Wilfried A.,Kitching, William
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p. 3479 - 3482
(2007/10/03)
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- Catalytic enantioselective synthesis of 2-alkylcyclobutanones and 4-alkyl-γ-butyrolactones from alkylidenecyclopropanes and the Sharpless AD-mix reagent
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Reaction of AD-mix with alkylidenecyclopropanes allows the synthesis of optically active 2-alkylcyclobutanones and 4-alkyl-γ-butyrolactones after stepwise pinacolic rearrangement and Beyer-Villiger oxidation.
- Krief, Alain,Ronvaux, Alain,Tuch, Arounarith
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p. 699 - 702
(2007/10/03)
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- Biotransformation of Oleic Acid to Optically Active γ-Dodecalactone
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We contemplated the formation of γ-dodecalactone through microbial conversion consisting of two steps, the first for oxidizing oleic acid into 10-hydroxystearic acid and the second for the formation of γ-dodecalactone from the hydroxy acid.Microorganisms were screened for production of 10-hydroxystearic acid from oleic acid.A bacterium which could produce the hydroxy acid with a transformation yield of 61.5percent at a concentration of 5percent oleic acid was isolated.The hydroxy acid was found to be biotransformed to γ-dodecalactone by baker's yeast.The enantiomeric composition of the biosynthetic γ-dodecalactone was estimated to be the (R)- configuration and the optical purity of the lactone was estimated to be 87.6percent e.e.The biotransformation yield from oleic acid to γ-dodecalactone was 22.5percent.
- Gocho, Shinobu,Tabogami, Nariyuki,Inagaki, Masao,Kawabata, Choko,Komai, Tuyosi
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p. 1571 - 1572
(2007/10/02)
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- Lipase-catalyzed Transesterification in organic Solvents: Preparation and Enantiodifferentiation of optically enriched 4(5)-alkylated 1,4(1,5)-olides
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Porcine pancreatic lipase (PPL) catalyzed intramolecular transesterification of n-propyl esters of 4(5)-hydroxyalkanoic acids (C5-C12) in diethyl ether (20 deg C) yielded (S)-4-alkylated 1,4-olides of high optical purity (ee > 80percent) and optically pure (R)-4-hydroxyalkanoic-n-propylesters, but exhibited low enantioselectivity for (S)-5-alkylated 1,5-olides (ee=10-20percent).The chiral analysis of 4(5)-hydroxyalkanoic esters was performed by HRGC and HPLC after their derivatization with (R)-(+)-1-phenylethylisocyanate, (S)-O-acetyllactic acid chloride, and (R)-(+)-α-methoxy-α-trifluoromethylphenylacetic acid chloride.The enantiodifferentiation of 1,4(1,5)-olides was achieved by HPLC on a chiral (ChiraSpher) using an on-line optical rotation detector (ChiraMonitor).
- Huffer, Manfred,Schreier, Peter
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p. 1157 - 1164
(2007/10/02)
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- Stereochemistry of the Microbial Generation of δ-Decanolide, γ-Dodecanolide, and γ-Nonanolide from C18 13-Hydroxy, C18 10-Hydroxy, and C19 14-Hydroxy Unsaturated Fatty Acids
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(S)-δ-Decanolide (4) was isolated from cultures of Cladosporium suaveolens after the microorganism was fed either (S)- or (R,S)-coriolic acid (1).Feeding (R,S)-10-hydroxyoctadec-(8E)-enoic acid (2) to Yarrowia lipolytica produced (S)-γ-dodecanolide.When (S)-homocoriolic acid (3) was fed to C. suaveolens, γ-nonalide slightly enriched in the S enantiomer was produced.At some stage in the biodegradation of 3, an inversion of configuration, from S to R, occured and was accompanied by the loss of the hydrogen atom originally present on C-14, as GLC/MS analysis of the products of feeding C. suaveolens with deuterated 10 showed.
- Cardillo, Rosanna,Fronza, Giovanni,Fuganti, Claudio,Grasselli, Piero,Mele, Andrea,et al.
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p. 5237 - 5239
(2007/10/02)
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- n-Pentenyl Glycosides as Mediators in the Asymmetric Synthesis of Monosubstituted Chiral Nonracemic Tetrahydrofurans and γ-Lactones
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n-Pentenyl glycosides can be oxidatively hydrolyzed by treatment with N-bromosuccinimide, previous work having been focused on the usefulness of the resulting glycosyl moiety.In this paper, attention is focused on asymmetric induction in the 2-(bromomethyl)furan that is liberated.The enantiomeric excess depends strongly on the orientations at the anomeric centers and at C2, as well as on the protecting group on the C2 oxygen. α-Anomers display higher asymmetric induction, and rationalization of this observation is based on the assumption that the molecule reacts from the favored ground-state orientation, wherein the exo anomeric effect is displayed.The usefulness of this route to optically active furans has been probed by a synthesis of an insect pheromone from the Bledius species.
- Llera, Jose Manuel,Lopez, J. Cristobal,Fraser-Reid, Bert
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p. 2997 - 2998
(2007/10/02)
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- Synthesis of both the enantiomers of 4-dodecanolide, the pheromone of the rove beetle
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A simple and efficient synthesis of the target pheromone in its enantiomeric forms has been formulated using easily accessible (R)-2,3- isopropanedioxyglyceraldehyde (2) as the single starting chiron.
- Chattopadhyay,Mamdapur,Chadha
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p. 3667 - 3672
(2007/10/02)
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- Lipase-Catalyzed Preparation of Optically Active γ-Butyrolactones in Organic Solvents
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Lipases in anhydrous organic solvents catalyze the lactonization of esters of γ-hydroxy carboxylic acids with a high degree of stereospecifity.Under these conditions the lipases exhibit both enantioselectivity and prochiral selectivity.We exploited the enzymes' enantioselectivity for synthesis of chiral lactones from racemic γ-hydroxy esters and their prochiral stereospecifity, i.e. the ability to discriminate between enantiotopic groups of a prochiral molecule, for the enantioconvergent lactonization of symmetrical γ-hydroxy diesters.This approach was used to develop a convenient, high yielding, and stereoselective route to several optically active γ-substituted γ-butyrolactones.
- Gutman, Arie L.,Zuobi, Kheir,Bravdo, Tamar
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p. 3546 - 3552
(2007/10/02)
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- Synthesis of the optical antipodes of 4-alkyl-γ-lactones
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Optical antipodes of 4-alkyl-γ-lactones 3 have been prepared by photochemical rearrangement of optically active α,β-epoxy diazomethyl ketones 1 in ethanol to give 4-hydroxy-alkenoates 2, followed by reduction of the alkene bond and subsequent lactonization.The required epoxy diazomethyl ketones 1 were obtained via the following sequence of reactions: alkylation of 2-propyn-1-ol, subsequent reduction to the alkenols 6, Sharpless epoxidation to 2,3-epoxy alcohols 7, oxidation to glycidic esters 8 and finally conversion to diazo ketones 1.The enantiomeric purities range from 84 to 100percent.
- Thijs, Lambertus,Waanders, Peter P.,Stokkingreef, Edwin H. M.,Zwanenburg, Binne
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p. 332 - 337
(2007/10/02)
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- KINETIC RESOLUTION OF LACTONES BY ENANTIOSELECTIVE PROTONATION OF THE CORRESPONDING CARBOXYLATE WITH A CHIRAL ACID
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Racemic lactones were optically activated through the hydrolysis with sodium hydroxide followed by the partial neutralisation with (1S)-(+)-10-camphorsulfonic acid in ethanol to afford R- or S-isomer with 99 - 38percent ee.
- Fuji, Kaoru,Node, Manabu,Murata, Makoto,Terada, Shunji,Hashimoto, Keiji
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p. 5381 - 5382
(2007/10/02)
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- Synthetic Applications of the Enantioselective Reduction by Binaphthol-Modified Lithium Aluminum Hydride Reagents
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The reduction of prochiral carbonyl substrates with the chiral binaphthol-modified lithium aluminum hydride reagents provides an effective means for preparing alcoholic products of high optical purity.The reaction is applicable to a variety of structurally diverse unsaturated carbonyl compounds such as aromatic ketones, acetylenic ketones, olefinic ketones and aldehydes, etc.Either of the antipodes is obtainable in a predictable manner by choosing the handedness of the auxiliary binaphthol ligand.The utility is exemplified by the efficiently stereocontrolled synthesis of prostaglandin intermediates, some insect pheromones, chiral primary terpenic alcohols, optically active styrene oxide, etc.
- Noyori, R.,Tomino, I.,Yamada, M.,Nishizawa, M.
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p. 6717 - 6725
(2007/10/02)
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- Synthesis of Both the Enantiomers of 4-Dodecanolide, a Defensive Secretion of Rove Beetles
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The enantiomers of 4-dodecanolide, a defensive secretion of rove beetles, were synthesized from (S)- and (R)-2-aminodecanoic acid obtained by the enzymic resolution of the corresponding chloroacetyl derivative.
- Sugai, Takeshi,Mori, Kenji
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p. 2497 - 2500
(2007/10/02)
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- Synthesis of Racemates and (+)-Enantiomers of γ-Caprolactone, γ-Dodecanolactone and δ-Hexadecanolactone, Lactonic Sex Pheromones of the Dermestid Beetle, Rove Beetle and Oriental Hornet
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A simple method based on regioselective two-step alkylation of easily-available diethyl 3-oxoglutarate (2) is described for the synthesis of racemates of the lactonic pheromones, 1a, 1b, and 1c.Their (+)-enantiomers were also synthesized by means of microbiological reduction of the intermediary keto acids.
- Naoshima, Yoshinobu,Ozawa, Hiroshi,Kondo, Hirokiyo,Hayashi, Shuichi
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p. 1431 - 1434
(2007/10/02)
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