cas 4873-09-0, ALLYL TOLUENE-4-SULFONATE | Articles data

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Preparation process of triallyl isocyanurate (by machine translation)
The preparation process is characterized in that allyl alcohol is used as a raw material, allyl alcohol and p-toluenesulfonyl chloride are prepared into allyl tosylate through an acid binding agent; and the prepared allyl tosylate is reacted with sodium cyanate, a phase transfer catalyst and a polar solvent to obtain triallyl isocyanurate. To the preparation method, allyl alcohol is adopted as the raw material, atmospheric pollution is reduced, the reaction rate is higher, the yield of triallyl isocyanurate is improved, the environment is protected, and the energy-saving and consumption-reducing effect is remarkable. (by machine translation)
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Paragraph 0010; 0013-0030

(2020/07/02)

Chiral tetraaryl-and tetraalkynylborates as chiral solvating agents for tetraalkylammonium salts
The application of tetracarbon-substituted chiral borate sodium salts (NaBR*4) as NMR chiral solvating agents for various tetraalkylammonium salts (R4NX) has been successfully demonstrated. Ion exchange between R4NX and NaBR*4 proceeded in excellent yields and provided the corresponding dia-stereomeric salts (R4NBR*4). The ee values of the R4NX salts were determined by1H NMR analysis of R4NBR*4. Two types of chiral borates, tetraaryl-and tetraalkynylborates with optically active 1,1′-binaphthyl components were used. At the beginning of this research, we investigated the efficacy of a known chiral tetraar-ylborate developed by Pommerening et al. for R4NX. To expand the possibility of further structural design of the chiral borate, we designed chiral tetraalkynylborates as a new structure. Their synthesis and application are also described.
Tayama, Eiji,Sugawara, Takeshi
supporting information
p. 803 - 811
(2019/01/18)

Facile synthesis of 1-Alkoxy-1H-benzo- and 7-azabenzotriazoles from peptide coupling agents, mechanistic studies, and synthetic applications
(1H-Benzo[d][1,2,3]triazol-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate (BOP), 1H-benzo[d][1,2,3]triazol-1-yl 4- methylbenzenesulfonate (Bt-OTs), and 3H-[1,2,3]triazolo[4,5-b]pyridine-3-yl 4-methylbenzenesulfonate (At-OTs) are classically utilized in peptide synthesis for amide-bond formation. However, a previously undescribed reaction of these compounds with alcohols in the presence of a base, leads to 1-alkoxy-1H-benzo- (Bt-OR) and 7-azabenzotriazoles (At-OR). Although BOP undergoes reactions with alcohols to furnish 1-alkoxy-1H-benzotriazoles, Bt-OTs proved to be superior. Both, primary and secondary alcohols undergo reaction under generally mild reaction conditions. Correspondingly, 1-alkoxy-1H-7-azabenzotriazoles were synthesized from At-OTs. Mechanistically, there are three pathways by which these peptide-coupling agents can react with alcohols. From 31P{1H}, [18O]-labeling, and other chemical experiments, phosphonium and tosylate derivatives of alcohols seem to be intermediates. These then react with BtO- and AtO- produced in situ. In order to demonstrate broader utility, this novel reaction has been used to prepare a series of acyclic nucleoside-like compounds. Because BtO- is a nucleofuge, several Bt-OCH2Ar substrates have been evaluated in nucleophilic substitution reactions. Finally, the possible formation of Pd πallyl complexes by departure of BtO- has been queried. Thus, alpha-allylation of three cyclic ketones was evaluated with 1-(cinnamyloxy)-1H-benzo[d][1,2,3]triazole, via in situ formation of pyrrolidine enamines and Pd catalysis.
Lakshman, Mahesh K.,Singh, Manish K.,Kumar, Mukesh,Chamala, Raghu Ram,Yedulla, Vijayender R.,Wagner, Domenick,Leung, Evan,Yang, Lijia,Matin, Asha,Ahmad, Sadia
p. 1919 - 1932
(2014/11/07)

Total synthesis of (+)-trienomycins A and F via C-C bond-forming hydrogenation and transfer hydrogenation
The triene-containing C17-benzene ansamycins trienomycins A and F were prepared in 16 steps (longest linear sequence, LLS) and 28 total steps. The C11-C13 stereotriad was generated via enantioselective Ru-catalyzed alcohol CH syn crotylation followed by chelation-controlled carbonyl dienylation. Enantioselective Rh-catalyzed acetylene-aldehyde reductive coupling mediated by gaseous H2 was used to form a diene that ultimately was subjected to diene-diene ring closing metathesis to form the macrocycle. The present approach is 14 steps shorter (LLS) than the prior syntheses of trienomycins A and F, and 8 steps shorter than any prior synthesis of a triene-containing C17-benzene ansamycin.
Del Valle, David J.,Krische, Michael J.
supporting information
p. 10986 - 10989
(2013/08/23)

Structure guided design of a series of sphingosine kinase (SphK) inhibitors
Sphingosine-1-phosphate (S1P) signaling plays a vital role in mitogenesis, cell migration and angiogenesis. Sphingosine kinases (SphKs) catalyze a key step in sphingomyelin metabolism that leads to the production of S1P. There are two isoforms of SphK and observations made with SphK deficient mice show the two isoforms can compensate for each other's loss. Thus, inhibition of both isoforms is likely required to block SphK dependent angiogenesis. A structure based approach was used to design and synthesize a series of SphK inhibitors resulting in the identification of the first potent inhibitors of both isoforms of human SphK. Additionally, to our knowledge, this series of inhibitors contains the only sufficiently potent inhibitors of murine SphK1 with suitable physico-chemical properties to pharmacologically interrogate the role of SphK1 in rodent models and to reproduce the phenotype of SphK1 (-/-) mice.
Gustin, Darin J.,Li, Yihong,Brown, Matthew L.,Min, Xiaoshan,Schmitt, Mike J.,Wanska, Malgorzata,Wang, Xiaodong,Connors, Richard,Johnstone, Sheere,Cardozo, Mario,Cheng, Alan C.,Jeffries, Shawn,Franks, Brendon,Li, Shyun,Shen, Shanling,Wong, Mariwil,Wesche, Holger,Xu, Guifen,Carlson, Timothy J.,Plant, Matthew,Morgenstern, Kurt,Rex, Karen,Schmitt, Joanna,Coxon, Angela,Walker, Nigel,Kayser, Frank,Wang, Zhulun
p. 4608 - 4616
(2013/08/15)

Copper-catalyzed trifluoromethylation and cyclization of aromatic-sulfonyl-group-tethered alkenes for the construction of 1,2-benzothiazinane dioxide type compounds
A multi-talented system: An efficient copper-catalyzed tandem trifluoromethylation/annulation of an electron-deficient aromatic ring has been developed. This method provides a powerful and straightforward way to synthesize trifluoromethylated 1,2-benzothiazinane dioxides under mild conditions (see scheme). The mechanism was investigated by a series of kinetic experiments and isotopic labeling studies.
Dong, Xiang,Sang, Rui,Wang, Qiang,Tang, Xiang-Ying,Shi, Min
supporting information
p. 16910 - 16915
(2014/01/06)

Synthesis of the cytotrienin A core via metal catalyzed C-C coupling
A synthetic approach to the C17-benzene ansamycins via metal catalyzed C-C coupling is described. Key bond formations include direct iridium catalyzed carbonyl crotylation from the alcohol oxidation level followed by chelation-controlled Sakurai-Seyferth dienylation to form the stereotriad, which is attached to the arene via Suzuki cross-coupling. The diene-containing carboxylic acid is prepared using rhodium catalyzed acetylene-aldehyde reductive C-C coupling mediated by gaseous hydrogen. Finally, ring-closing metathesis delivers the cytotrienin core.
Roessle, Michael,Del Valle, David J.,Krische, Michael J.
supporting information; experimental part
p. 1482 - 1485
(2011/05/15)

ZnO and ZnO-nanoparticles: Efficient and reusable heterogeneous catalysts for one-pot synthesis of N-acylsulfonamides and sulfonate esters
Commercially available and preparative ZnO nanoparticles are reported as efficient and reusable catalysts for the chemoselective synthesis of N-acylsulfonamides and sulfonate esters. A one-pot sequential sulfonylation and acylation of amines took place to afford the N-acylsulfonamides in excellent yields under solvent-free conditions. The ZnO catalyst can be reused for without significant loss of catalytic activity.
Tamaddon, Fatemeh,Sabeti, Mohammad Reza,Jafari, Abbas Ali,Tirgir, Farhang,Keshavarz, Elham
experimental part
p. 41 - 45
(2012/01/12)

Novel polymeric nonionic photoacid generators and corresponding polymer Langmuir-Blodgett (LB) films for photopatterning
A series of new polymeric nonionic photoacid generators (PAGs) and PAG-bound polymers designed for photoresist materials in Langmuir-Blodgett (LB) films have been synthesized and characterized. The novel polymer could form a stable and condensed monolayer on water surface, which could be transferred successfully onto solid substrate. Upon deep UV irradiation, the acid generated by the photoacid generator catalyzed the naphthyl moiety to liberate naphthol and regenerate carboxyl in the exposed region. The rent moiety could dissolve in alkaline aqueous, resulting in a fine positive tone resist patterns with a resolution of 0.75 μm. Sensitivity curves and TGA studies revealed that the high sensitivity in 248 nm irradiation was attributed to the present of PAG units incorporated in the polymer chains. The result of translated gold pattern with the same resolution as the resist pattern also demonstrated that the resist LB films had sufficient resistance to wet etching process.
Xu, Wenjian,Li, Tiesheng,Li, Gaojian,Wu, Yangjie,Miyashita, Tokuji
experimental part
p. 50 - 57
(2012/01/14)

Expedient route to the functionalized calyciphylline a- Type skeleton via a michael addition- RCM strategy
An efficient, robust, and scalable strategy to access the functionalized core of calyciphylline A-type alkaloids has been developed starting from commercially available 3-methylanisole. Key features of this approach are an intramolecular Michael addition/allylation sequence and a ringclosing metathesis step.
Sladojevich, Filippo,Michaelides, Iacovos N.,Darses, Benjamin,Ward, John W.,Dixon, Darren J.
supporting information; experimental part
p. 5132 - 5135
(2011/12/15)

Regioselective alkylation of hydroxysalicylaldehydes
Schiff-base ligands are often used as backbone ligands for mono- and dinuclear complexes that serve as catalysts during aerobic oxidation reactions. However, their water solubility is low and limits their applicability as catalysts to transform highly water-soluble biomolecules, such as carbohydrates or amino alcohols. A new method to regioselectively incorporate water solubility-promoting polyethylene glycol side chains into a frequently used aldehyde building block of Schiff-base ligands has been developed.
Gichinga, Moses G.,Striegler, Susanne
supporting information; experimental part
p. 4917 - 4922
(2009/10/02)

Amphiphilic organocatalyst for schotten-baumann-type tosylation of alcohols under organic solvent free condition
A Tosylation of primary alcohol with tosyl chloride was performed effectively with an W-hexadecylimidazole catalyst in water containing K 2CO3 aggregation of the catalyst carrying a hydrophobic methylene chain worked as a substitute for organic solvent.
Asano, Keisuke,Matsubara, Seijiro
supporting information; experimental part
p. 1757 - 1759
(2009/09/06)

Stereoselective synthesis of bioactive isosteviol derivatives as α-glucosidase inhibitors
Considerable interest has been attracted in isosteviol and its derivatives because of their large variety of pharmacological activities. In this project, a series of novel compounds containing hydroxyl, hydroxymethyl group and heteroatom-containing frameworks fused with isosteviol structure were synthesized and evaluated as α-glucosidase inhibitors, aimed at clarifying the structure-activity correlation. The results indicated that these isosteviol derivatives were capable of inhibiting in vitro α-glucosidase with moderate to good activities. Among them, indole derivative 15b exhibited the highest activities and thus may be exploitable as a lead compound for the development of potent α-glucosidase inhibitors.
Wu, Ya,Yang, Jing-Hua,Dai, Gui-Fu,Liu, Cong-Jun,Tian, Guo-Qiang,Ma, Wen-Yan,Tao, Jing-Chao
experimental part
p. 1464 - 1473
(2009/09/05)

Palladium-catalyzed cyclopentenone formation by carbonylative cycloaddition of allylic tosylates and alkynes
Carbonylative cycloaddition of allyl tosylates and alkynes proceeded in the presence of palladium catalysts to afford a range of cyclopentenones. In the presence of methanol, five-component coupling reactions gave methyl cyclopentenyl acetates, whereas in the absence of methanol, (cyclopentenoylmethylidene)furanones were formed from six components. Allyl tosylate was found to be essential for these reactions, as allyl acetate and allyl bromide proved to be ineffective. Georg Thieme Verlag Stuttgart.
Tsukada, Naofumi,Sugawara, Shuichi,Okuzawa, Tomohiro,Inoue, Yoshio
p. 3003 - 3008
(2008/02/10)

A ring-closing metathesis pathway to fluorovinyl-containing nitrogen heterocyles
The synthesis of highly functionalized fluorinated piperidines is described. The key step in this synthesis is a ring-closing metathesis reaction involving fluoride-substituted olefins, which leads to the corresponding cyclic vinyl fluorides. Several sequences to arrive at differently substituted piperidines have been evaluated. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
De Matteis, Valeria,Van Delft, Floris L.,Tiebes, Joerg,Rutjes, Floris P. J. T.
p. 1166 - 1176
(2007/10/03)

An efficient one-pot conversion of THP and TMS ethers to sulfonate esters using FeCl3-montmorillonite K-10 clay
Various tetrahydropyranyl and trimethylsilyl ethers are efficiently transformed into the corresponding sulfonate esters with sulfonyl chlorides in the presence of FeCl3-Montmorillonite K-10 clay.
Movassagh, Barahman,Shokri, Salman
p. 763 - 765
(2007/10/03)

Montmorillonite clay catalyzed tosylation of alcohols and selective monotosylation of diols with p-toluenesulfonic acid: An enviro-economic route
An enviro-economic route for tosylation of alcohols and selective monotosylation of diols in good yield directly using p-toluenesulfonic acid together with metal-exchanged montmorillonite instead of p-toluenesulfonyl chloride or p-toluenesulfonic anhydrid
Choudary, Boyapati M.,Chowdari, Naidu S.,Kantam, Mannepalli L.
p. 7291 - 7298
(2007/10/03)

Effect of the leaving group on the alkylation diastereoselectivity of the Schollkopf chiral auxiliary
Tosylates, diphenylphosphates and bromides were employed to study the effect of the leaving group on the alkylation diastereoselectivity of the Schollkopf chiral auxiliary 1 at aliphatic, benzylic, propargylic and allylic electrophilic centers. The diastereoselectivity generally follows the pattern: diphenylphosphate > tosylate > bromide. In terms of both diastereoselectivity and yield, each leaving group possesses a different advantage.
Ma, Chunrong,He, Xiaohui,Liu, Xiaoxiang,Yu, Shu,Zhao, Shuo,Cook, James M.
p. 2917 - 2918
(2007/10/03)

Practical and Safe Sulfonylation of 2-Alkynyl and 2-Alkenyl Alcohols Using the Combined Bases of a Catalytic Amount of Tertiary Amine and Potassium Carbonate
Several 2-alkynyl and 2-alkenyl alcohols were effectively sulfonylated with methanesulfonyl chloride or p-toluenesulfonyl chloride using the combined bases of a catalytic amount of tertiary amine and potassium carbonate.The reaction was conducted with reliable safety and while avoiding the disposal of wasted amines.The mesylation of 2-propyn-1-ol proceeded on a large scale (more than 20 kg) without a substantial production of explosive 3-chloro-1-propyne.The choice of the catalysts was important, and sterically unhindered tertiary amines, such as trimethylamine, N,N-d imethylbenzylamine, and triethylamine, were effective.Without these catalysts the reactions were significantly retarded.The reaction was so mild that it could be applied to complex and optically active 4-hydroxy-3-methyl-2-(2-propynyl)-2-cyclopenten-1-one, which is an important alcohol moiety of synthetic pyrethroids.
Tanabe, Yoo,Yamamoto, Hitomi,Yoshida, Yoshihiro,Miyawaki, Takashi,Utsumi, Naoka
p. 297 - 300
(2007/10/02)

Synthesis of Enantiomerically Pure Unsaturated α-Amino Acids Using Serine-Derived Zinc/Copper Reagents
Treatment of the serine-derived organozinc reagent 2, in benzene/dimethylacetamide, with a THF solution of CuCN*2LiCl gives rise to a zinc/copper reagent 6 which reacts directly with allylic halides and tosylates to give the corresponding enantiomerically pure substitution products 9 in 32-65percent yield (11 examples).The reaction proceeds by formal SN2' displacement of the leaving group.Reaction with propargyl halides gives the corresponding terminal allene 12a.The zinc reagent 2 may also be prepared directly from protected iodoalanine 1 in THF by the Knochel method.Reaction with propargylic tosylates as electrophiles gives rise to the corresponding protected terminal allenic amino acids in 51-81percent yield (four examples); use of enantiomerically enriched propargylic tosylates results in the formation of diastereoisomerically enriched allenic products.Reactions of the zinc/copper reagent 6 with a range of representative electrophiles is explored; use of relatively reactive electrophiles is necessary to obtain satisfactory yields.Finally, the possibility of using the serine-derived iodide 20, in which the carboxylic acid is protected as a methyl ester, is established.This reagent offers advantages over the corresponding benzyl ester protected reagent 6 for the synthesis of unsaturated amino acids.
Dunn, Michael J.,Jackson, Richard F. W.,Pietruszka, Joerg,Turner, Debra
p. 2210 - 2215
(2007/10/02)

Synthesis of δ-L-α-aminoadipoyl-L-cysteinyl- D-allylglycine, and eight deuterated analogues, substrates for the investigation of the mechanism of action of isopenicillin n synthase
The synthesis of δ-L-α-aminoadipoyl-L-cysteinyl-D-allylglycine (1a) from its component amino acids is described, along with the synthesis of eight analogues (1b-i) specifically deuterated at C-3 and/or C-5 of the allyglycine residue.
Baldwin, Jack E.,Bradley, Mark,Turner, Nicholas J.,Adlington, Robert M.,Pitt, Andrew R.,Sheridan, Helen
p. 8203 - 8222
(2007/10/02)

Sulphonate Esters as Sources of Sulphonyl Radicals; Ring-closure Reactions of Alk-4- and -5-enesulphonyl Radicals
Alkyl alkanesulphonates and arenesulphonates were found to be useful sources of sulphonyl radicals, particularly for spectroscopic work, when treated with organotin or organosilyl radicals.Allyl, propynyl and penta-2,4-dienyl methanesulphonates gave, however, allyl, propynyl and pentadienyl radicals, respectively.Sulphonyl radicals generated in this way added efficiently to alk-1-enes with electron-releasing substituents, and the EPR spectra of the adduct radicals were recorded.A variety of radical initiation systems were tried on pent-4-enesulphonyl chloride.The pent-4-enesulphonyl radical cyclised mainly in the endo mode to give the six-membered-ring sulphone.Similarly, the hex-5-enesulphonyl radical cyclised to give thiepane 1,1-dioxide, with a seven-membered ring.The cyclohex-2-enylethanesulphonyl radical cyclised mainly in the exo mode to give 2-chloro-9-thiabicyclononane 9,9-dioxide.The mechanisms of these reactions are discussed.
Culshaw, Peter N.,Walton, John C.
p. 1201 - 1208
(2007/10/02)

Anodic Oxidation of (Trimethylsilyl)methanes with ?-Electron Substituents in the Presence of Nucleophiles
It was found that oxidation potentials of methanes with ?-electron substituents were decreased by introduction of a trimethylsilyl group.The anodic oxidation of benzyl-, allyl-, aryl(or alkyl)thiomethyl-, and aryloxymethyl-substituted trimethylsilanes smoothly proceeded in the presence of nucleophiles, e.g. alcohols and carboxylic acids, to eliminate the trimethylsilyl groups giving the corresponding alkoxylated and carboxylated products in moderate or high yields without full optimization of electrolytic conditions, while aminomethylsilanes did not undergo such a kind of anodic oxidation.
Koizumi, Toshio,Fuchigami, Toshio,Nonaka, Tsutomu
p. 219 - 225
(2007/10/02)

Cope Rearrangement in the Thiophene Series
The inability to observe Cope rearrangement at elevated temperature for diethyl α-allylphenylmalonate does not extend to the analogous systems resulting from replacement of the benzene ring by 2- and 3-thiophene nuclei.Thermal rearrangement of diethyl α-allyl-2-thienylmalonate (5) at 250-260 deg C for 12 h produces the expected Cope rearrangement product diethyl (3-allyl-2-thienyl)malonate (6) (49percent) accompanied by ethyl 6-carboethoxy-5,6-dihydro-4H-5-cyclopentathiopheneacetate (7) (28percent).The structural verification of 6 was obtained by degradation to 3-allyl-2-methylthiophene which was compared with an authentic sample obtained by synthesis.The structure of 7 was based on analogy.Similar results were observed with the 3-substituted analogues of 5, both diethyl (2-allyl-3-thienyl)malonate (14) and ethyl 4-carboethoxy-5,6-dihydro-4H-5-cyclopentathiopheneacetate (15) being formed.In this case the structure of 14 was verified by synthesis.Speculative mechanistic considerations are offered regarding the mode of transformation of 6 to 7 and 14 to 15.That the methine proton of the malonate substituent in 6 and 14 is involved in this transformation is seen by the inability of the appropriate methyl-substituted derivative of 6 to undergo thermal cyclization.
MacDowell, Denis W. H.,Purpura, Joseph M.
p. 183 - 188
(2007/10/02)

CORRELATION OF THE RATES OF SOLVOLYSIS OF ALLYL AND BENZYL ARENESULPHONATES
Analysis of the specific rates of solvolysis of allyl arenesulphonates in terms of the extended Grunwald-Winstein equation indicates a marked dependence on both the solvent nucleophilicity (high/value) and the solvent ionizing power (high m value).As the charge delocalization in the leaving group increases, both l and m values fall.For allyl toluene-p-sulphonate solvolysis in 28 solvents at 50.0 deg C, values for l(0.83) and for m (0.63), based on the use of NKL and Y values, are very similar to the equivalent values of 0.90 and 0.67 previously reported for benzyl toluene-p-sulphonate solvolysis.Related extended Grunwald-Winstein analyses are considered and the need for variety in the choice of solvents is emphasized.
Kevill, Dennis N.,Rissmann, Thomas J.
p. 717 - 720
(2007/10/02)