- Production of dynamic lipid bilayers using the reversible thiol-thioester exchange reaction
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Thiol lysolipids undergo thiol-thioester exchange with two phenyl thioester-functionalized tails to produce phospholipid structures that assemble into liposomes with differences in exchange rates, temperature sensitivity, permeability, and continued excha
- Konetski, Danielle,Mavila, Sudheendran,Wang, Chen,Worrell, Brady,Bowman, Christopher N.
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supporting information
p. 8108 - 8111
(2018/07/29)
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- One for Many: A Universal Reagent for Acylation Processes
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This work describes acylation reactions facilitated by a type of heterocycle-based acyl transfer agent, 2-acyloxypyridazinone. Reactions of 2-acyloxypyridazinone with carboxylic acids yield mixed carbonic anhydride intermediates, which are reactive and could be coupled with a wide range of substrates including acids, amines, alcohols, and thiols. The wide substrate scope, ease of operation (no additive or catalyst), storage and handling stability, and atom-efficiency from recycling the heterocycle carrier make the reported acylating agent attractive for acylation-based coupling reactions.
- Moon, Hyun Kyung,Sung, Gi Hyeon,Kim, Bo Ram,Park, Jong Keun,Yoon, Yong-Jin,Yoon, Hyo Jae
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supporting information
p. 1725 - 1730
(2016/06/09)
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- Fast and highly chemoselective alkynylation of thiols with hypervalent iodine reagents enabled through a low energy barrier concerted mechanism
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Among all functional groups, alkynes occupy a privileged position in synthetic and medicinal chemistry, chemical biology, and materials science. Thioalkynes, in particular, are highly useful, as they combine the enhanced reactivity of the triple bond with a sulfur atom frequently encountered in bioactive compounds and materials. Nevertheless, general methods to access these compounds are lacking. In this article, we describe the mechanism and full scope of the alkynylation of thiols using ethynyl benziodoxolone (EBX) hypervalent iodine reagents. Computations led to the discovery of a new, three-atom concerted transition state with a very low energy barrier, which rationalizes the high reaction rate. On the basis of this result, the scope of the reaction was extended to the synthesis of aryl- and alkyl-substituted alkynes containing a broad range of functional groups. New sulfur nucleophiles such as thioglycosides, thioacids, and sodium hydrogen sulfide were also alkynylated successfully to lead to the most general and practical method yet reported for the synthesis of thioalkynes.
- Frei, Reto,Wodrich, Matthew D.,Hari, Durga Prasad,Borin, Pierre-Antoine,Chauvier, Clment,Waser, Jrme
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supporting information
p. 16563 - 16573
(2015/01/09)
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- The mechanism of caseinolytic protease (ClpP) inhibition
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Catch me if you can: The ClpP protease mediates protein homeostasis and can be efficiently inhibited by β-lactones. A combination of molecular docking, mutagenesis, activity-based protein profiling, and kinetics studies now reveals the mechanism of ClpP inhibition. A hydrophobic pocket next to the active site allows binding of long aliphatic and aromatic residues. The preferred stereoisomer binds into the oxyanion hole. Copyright
- Gersch, Malte,Gut, Felix,Korotkov, Vadim S.,Lehmann, Johannes,B?ttcher, Thomas,Rusch, Marion,Hedberg, Christian,Waldmann, Herbert,Klebe, Gerhard,Sieber, Stephan A.
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supporting information
p. 3009 - 3014
(2013/04/23)
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- Acid-Catalyzed Regioselective Acylation of α-Silylallylic Sulfides and Its Application to a Novel Cyclopentannelation and Furan Annelation
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Introduction of a silyl group at the α-position of allylic sulfides, followed by the aluminum chloride-catalyzed reaction of the resulting α-silylallylic sulfides with acid chlorides resulted in regioselective acylation at the γ-position of the allylic system to give γ-acylated vinylic sulfides, chemically equivalent to 1,4-dicarbonyl compounds.Heating of the products in refluxing benzene with an equimolar amount of p-toluenesulfonic acid produced 2-cyclopentanone derivatives.Treatment of the acylated products with an equimolar amount of concentrated sulfuric acid gave α-phenylthiofuran derivatives.These procedures provide a novel method for cyclopentannelation and furan annelation.Keywords - α-silylallylic sulfide; acid chloride; aluminum chloride; acid-catalyzed acylation; vinylic sulfide; 2-cyclopentanone; α-phenylthiofuran; furan; cyclopentannelation; furan annelation
- Hiroi, Kunio,Sato, Hiroyasu,Chen, Lih-Ming,Kotsuji, Kumiko
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p. 1413 - 1426
(2007/10/02)
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- A NOVEL METHOD FOR CYCLOPENTANNELATION USING REGIOSELECTIVE ACYLATION OF ALLYLIC SULFIDES VIA α-SILYL INTERMEDIATES
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An aluminum chloride-catalyzed reaction of 1-(phenylthiotrimethylsilylmethyl)cyclohexene, readily obtainable from cyclohexanone, with acid chlorides in dichloromethane underwent a regioselective acylation at the γ-position of the allylic system to give γ-acyl enol thioethers in good yields.Heating of these enol thioethers with an equimolar amount of p-toluenesulfonic acid produced 2-cyclopentenone derivatives.This novel method for cyclopentannelation provides a new entry to 2-cyclopentenone ring systems.
- Hiroi, Kunio,Sato, Hiroyasu,Kotsuji, Kumiko
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p. 743 - 746
(2007/10/02)
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- -Sigmatropic Rearrangement of an in Situ Prepared Ylide and a Thioether to Thio Ester Conversion as Key Steps in Short Syntheses of Sarkomycin and Its Phenylthio Ester
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2-cyclopent-2-en-1-one (2), which is readily available by the reaction of 2-cyclopentenone with thiophenol, formaldehyde, and triethylamine, is transformed, in high yield and moderate conversion by treatment with (trimethylsilyl)methyl triflate, cesium fluoride, and benzaldehyde, to 2-methylene-3-cyclopentanone (3), which, by the use of trichloroisocyanuric acid (Chloreal), can be quantitatively dichlorinated on the sulfur-bearing carbon atom to 3--2-methylenecyclopentanone (4).This dichloro thioether could be hydrolyzed in good yield to a mixture of sarkomycin phenyl thio ester (5) and sarkomycin (6), containing mainly the former; an additional small amount of sarkomycin can be obtained by hydrolysis of the thio ester in the presence of silver trifluoroacetate and benzhydrol.This procedure represents one of the shortest extant syntheses of sarkomycin and a sarkomycin ester.Model studies of the dichlorination of n-octyl phenyl sulfide (8) to 1-(phenylthio)-1,1-dichlorooctane (9) and various transformations of the latter are also reported.
- Cohen, Theodore,Kosarych, Zenyk,Suzuki, Kunio,Yu, Lin-Chen
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p. 2965 - 2968
(2007/10/02)
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- A HIGHLY EFFICIENT SYNTHETIC ROUTE TO KETONES THROUGH SEQUENTIAL COUPLING REACTIONS OF GRIGNARD REAGENTS WITH S-PHENYL CARBONOCHLORODITHIOATE IN THE PRESENCE OF NICKEL OR IRON CATALYSTS
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The sequential coupling reactions of Grignard reagents with S-phenyl carbonochloridothioate in the presence of nickel(II) or iron(III) catalysts provides a very mild and straightforward route to symmetrical and unsymmetrical aliphatic and aromatic ketones.
- Cardellicchio, C.,Fiandanese, V.,Marchese, G.,Ronzini, L.
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p. 3595 - 3598
(2007/10/02)
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- DI-2-PYRIDYL CARBONATE: A NEW EFFICIENT COUPLING AGENT FOR THE DIRECT ESTERIFICATION OF CARBOXYLIC ACIDS
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Reaction of carboxylic acids with equimolar amounts of di-2-pyridyl carbonate and alcohols or thiols in the presence of 4-dimethylaminopyridine as a catalyst in methylene chloride at room temperature affords the corresponding esters in high yields under mild conditions.
- Kim, Sunggak,Lee, Jae In,Ko, Young Kwan
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p. 4943 - 4946
(2007/10/02)
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