- Palladium-Catalyzed Thiocarbonylations with Triisopropylsilyl Thioethers
-
We have developed a palladium-catalyzed thiocarbonylation through the reaction of a σ-alkyl palladium intermediate with carbon monoxide and a triisopropylsilyl (TIPS) thioether. The use of CsF, (IPr)Pd(allyl)Cl [IPr =1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene], CO, and a TIPS thioether in THF are key to obtaining alkyl and aryl thioesters in high yields. The yield of the palladium-catalyzed thiocarbonylation depended on the structure of the substrate; indoline-2-one derivatives were formed faster than indoline derivatives. The reactions of benzoyl and hydrocinnamoyl fluorides with TIPSSPh and CsF also gave the corresponding thioesters.
- Hosoya, Yosuke,Mizoguchi, Kota,Yasukochi, Honoka,Nakada, Masahisa
-
p. 495 - 501
(2022/02/16)
-
- Manganese(iii)-promoted thiocarbonylation of alkylborates with disulfides: synthesis of aliphatic thioesters
-
A Mn(iii)-promoted thiocarbonylation procedure toward the synthesis of thioesters has been developed. By employing easily available disulfides and potassium alkyltrifluoroborates as the starting materials, and cheap and non-toxic Mn(OAc)3·2H2O as the promotor, a broad range of thioesters were synthesized in good to excellent yieldsviaradical intermediates.
- Chen, Bo,Wu, Xiao-Feng
-
supporting information
p. 9654 - 9658
(2021/12/01)
-
- Palladium-catalyzed thiocarbonylation of alkenes toward linear thioesters
-
Thiocarbonylation of alkenes offers an ideal procedure for the synthesis of thioesters. However, thiocarbonylation of alkenes, especially styrenes, to produce valuable linear thioesters has remained a challenge. In this Letter, a general palladium-catalyz
- Ai, Han-Jun,Zhao, Fengqian,Geng, Hui-Qing,Wu, Xiao-Feng
-
p. 3614 - 3619
(2021/04/07)
-
- ANTIBACTERIAL BETA-LACTONES, AND METHODS OF IDENTIFICATION, MANUFACTURE AND USE
-
The invention encompasses antibacterial beta-lactones, methods of making, pharmaceutical preparations thereof, and methods of utilization of such compounds for the treatment of bacterial infections.
- -
-
Page/Page column 11-12
(2015/03/16)
-
- Comprehensive Study of the Organic-Solvent-Free CDI-Mediated Acylation of Various Nucleophiles by Mechanochemistry
-
Acylation reactions are ubiquitous in the synthesis of natural products and biologically active compounds. Unfortunately, these reactions often require the use of large quantities of volatile and/or toxic solvents, either for the reaction, purification or isolation of the products. Herein we describe and discuss the possibility of completely eliminating the use of organic solvents for the synthesis, purification and isolation of products resulting from the acylation of amines and other nucleophiles. Thus, utilisation of N,N′-carbonyldiimidazole (CDI) allows efficient coupling between carboxylic acids and various nucleophiles under solvent-free mechanical agitation, and water-assisted grinding enables both the purification and isolation of pure products. Critical parameters such as the physical state and water solubility of the products, milling material, type of agitation (vibratory or planetary) as well as contamination from wear are analysed and discussed. In addition, original organic-solvent-free conditions are proposed to overcome the limitations of this approach. The calculations of various green metrics are included, highlighting the particularly low environmental impact of this strategy.
- Mtro, Thomas-Xavier,Bonnamour, Julien,Reidon, Thomas,Duprez, Anthony,Sarpoulet, Jordi,Martinez, Jean,Lamaty, Frdric
-
supporting information
p. 12787 - 12796
(2015/09/01)
-
- Tetraethylammonium bromide-catalyzed oxidative thioesterification of aldehydes and alcohols
-
A metal-free, tetraethylammonium bromide-catalyzed oxidative coupling of aldehydes or alcohols with thiophenols or disulfides has been developed. This protocol affords an efficient and inexpensive approach to the synthesis of a wide range of thioesters in high yields. Copyright
- Zhu, Xuebin,Shi, Yan,Mao, Haibin,Cheng, Yixiang,Zhu, Chengjian
-
supporting information
p. 3558 - 3562
(2014/01/06)
-
- Fe-catalyzed thioesterification of carboxylic esters
-
Second nature: Starting from shelf-stable aryl esters and thiols, a variety of carboxylic acid esters were transformed into the corresponding thioesters with no racemization of labile stereocenters (see scheme). The method was successfully applied in a native chemical-ligation-type peptide formation, which suggests that the thiol may act as a co-catalyst for future 1,2-additions of pronucleophiles to carboxylic esters.
- Magens, Silja,Plietker, Bernd
-
p. 8807 - 8809
(2011/09/16)
-
- Mild, powerful, and robust methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively
-
We developed two efficient practical methods for esterification, amide formation, and thioesterification between acid chlorides and alcohols, amines, thiols, respectively. The present mild and robust reaction was performed by two separate methods both by combining cheap and readily available amines, N-methylimidazole, and N,N,N′,N′-tetramethylethylenediamine (TMEDA). Method A uses catalytic N-methylimidazole and TMEDA with an equimolar amount of K2CO3, whereas Method B uses equimolar amounts of N-methylimidazole and TMEDA. The salient features are as follows. (i) With regard to reactivity, Method B was superior to Method A for esterification and thioesterification, whereas cost-effective Method A was superior to Method B for amide formation. (ii) Amide formation proceeded smoothly between acid chlorides and less nucleophilic and stereocongested amines such as 2,6-dichloroaniline. (iii) This protocol was applied to the successful synthesis of two agrochemicals, bromobutide and carpropamid.
- Nakatsuji, Hidefumi,Morimoto, Mami,Misaki, Tomonori,Tanabe, Yoo
-
p. 12071 - 12080
(2008/03/13)
-
- A convenient method for the synthesis of carboxamides and thioesters by using tetrakis(2-methylimidazol-1-yl)silane
-
Tetrakis(2-methylimidazol-1-yl)silane [Si(2-Me-Im)4], a new dehydrating reagent having silicon-imidazole linkage, reacted readily with carboxylic acids at room temperature to form the corresponding 1-acyl-2-methylimidazole intermediates, which smoothly underwent subsequent condensation with nucleophiles such as amines or thiols to afford the corresponding carboxamides or thioesters in good to excellent yields, respectively.
- Tozawa, Takashi,Yamane, Yoshinobu,Mukaiyama, Teruaki
-
p. 629 - 641
(2007/10/03)
-
- Efficient synthesis of thioesters and amides from aldehydes by using an intermolecular radical reaction in water
-
The combination of the water-soluble radical initiator, 2,2′-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (VA-044) and the surfactant, cetyltrimethyl-ammonium bromide (CTAB), was found to be the most suitable condition for the effective and direct synthesis of useful active thioesters (pentafluorophenyl thioesters) in water. In addition, the direct amidation of aldehydes was achieved by the addition of the amines to the thioesterification reaction mixture in water.
- Nambu, Hisanori,Hata, Kayoko,Matsugi, Masato,Kita, Yasuyuki
-
p. 719 - 727
(2007/10/03)
-
- Simple, Mild, and Practical Esterification, Thioesterification, and Amide Formation Utilizing p-Toluenesulfonyl Chloride and N-Methylimidazole
-
We have developed an efficient method for the esterification or thioesterification of equimolar amounts of carboxylic acids and alcohols or thiols using a novel reagent, p-toluenesulfonyl chloride (TsCl) together with N-methylimidazole. The present method is simple, mild, and reactive, uses readily available and economical reagents. The choice of amine is critical for the present method. The amine, N-methylimidazole, has two roles: (i) as an HCl scavenger for the initial smooth generation of mixed anhydrides between carboxylic acids and TsCl and (ii) successive formation of highly reactive ammonium intermediates from mixed anhydrides. This method could be applied to various types of carboxylic acids, alcohols, and thiols: a) several functionalities were tolerated; b) two N-Cbz amino acids were smoothly esterified without racemization; and c) the labile 1β-methylcarbapenem key intermediate and a pyrethroid insecticide, prallethrin, were successfully prepared. The related amide formation between carboxylic acids and primary or secondary amines was also performed. The proposed reaction mechanism involves a novel method for producing the reactive acylammonium intermediates. The production of these intermediates was rationally supported by a careful 1H NMR monitoring study.
- Wakasugi, Kazunori,Iida, Akira,Misaki, Tomonori,Nishii, Yoshinori,Tanabe, Yoo
-
p. 1209 - 1214
(2007/10/03)
-
- A New and Efficient Esterification Reaction via Mixed Anhydrides by the Promotion of a Catalytic Amount of Lewis Acid
-
In the presence of a catalytic amount of Lewis acid, various carboxylic esters or S-phenyl carbothioates are prepared in excellent yields by the respective reactions of equimolar amounts of silyl carboxylates and alkyl silyl ethers or phenyl silyl sulfides with 4-trifluoromethylbenzoic anhydride.
- Miyashita, Mitsutomo,Shiina, Isamu,Miyoshi, So,Mukaiyama, Teruaki
-
p. 1516 - 1527
(2007/10/02)
-
- Synthesis and reactivity of iron carbonyl complexes of α,β-unsaturated acyl silanes
-
2-Trimethylsilyl-1-oxa-1,3-butadiene (7) reacts with Fe2(CO)9 to form an unstable tetracarbonyliron (0) complex (8) whereas 2-trimethylsilyl-4-phenyl-1-oxa- 1-oxa-1,3-butadiene (9) and 2-(tert-butyldimethylsilyl)-4-phenyl-1-oxa-1,3-butadiene (20) react with Fe2(CO)9 to form highly stable crystalline tricarbonyliron(0) complexes (16 and (21). Complexes (16) and (21) both undergo acylation when reacted with methyl lithium under nitrogen to form γ-ketoacylsilanes [(18) and (22)], but only complex (21) reacts with methyl lithium under carbon monoxide to give the tricarbonyl(vinylketene)iron(0) complex (23).
- Thomas, Susan E.,Tustin, Gary J.,Ibbotson, Arthur
-
p. 7629 - 7640
(2007/10/02)
-
- A New and Efficient Method for the Preparation of S-Phenyl Carbothioates via Mixed Anhydrides Using Active Titanium(IV) Salts
-
In the presence of a catalytic amount of titanium(IV) salt, various S-phenyl carbothioates are prepared in excallent yields by the reaction of nearly equimolar amounts of silyl derivatives of carboxylic acids and benzenethiols with p-trifluoromethylbenzoic anhydride.
- Mukaiyama, Teruaki,Miyashita, Mitsutomo,Shiina,, Isamu
-
p. 1747 - 1750
(2007/10/02)
-
- AROMATIC ANNULATION WITH BISPHENYLTHIONIUM IONS
-
The chemospecific production and intramolecular aromatic electrophilic substitution (annulation) of bis(phenylthio)carbocations (bisphenylthionium ions) has been studied using appropriate model compounds.The annulation reaction is very sensitive to the Lewis acid initiator and also the solvent.The best reaction conditions were found to be a suspension of silver trifluoromethanesulfonate in dichloromethane.Annulation of six-membered rings onto alkylbenzene and five- and seven-membered rings onto activated benzenes have been achieved.
- Manas, Abdul Rahman Bin,Smith, Robin A. J.
-
p. 1847 - 1856
(2007/10/02)
-
- A Method for Mild Photochemical Oxidation; Conversion of Phenacyl Sulfides into Carbonyl Compounds
-
Sunlamp irradiation of phenacyl sulfides PhCOCH2SCHRR' affords thiocarbonyl compounds S=CRR' that can be trapped in high yield by using the nitronate CH3CH=N+(OTBS)O-; the heterocycle 3 resulting from 1,3-dipolar cycloaddition is cleaved rapidly by fluoride ion to give ketones or aldehydes.
- Vedejs, E.,Perry, D. A.
-
p. 573 - 575
(2007/10/02)
-