36195-56-9Relevant academic research and scientific papers
Direct oxidative allylic and vinylic amination of alkenes through selenium catalysis
Trenner, Johanna,Depken, Christian,Weber, Thomas,Breder, Alexander
supporting information, p. 8952 - 8956 (2013/09/02)
Bringing "N" into the game: The direct chemoselective nitrogenation of unactivated alkenes can be achieved through oxidative selenium catalysis (see scheme). This method provides a broad variety of allylic imides in yields of up to 89 % using N-fluorobenzenesulfonimide (NFSI) as the terminal oxidant and nitrogen source. Furthermore, an unprecedented selenium-catalyzed vinylic C(sp2)-H nitrogenation was discovered. Copyright
Silica nanoparticles as a reusable catalyst: A straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts under neutral reaction conditions
Banerjee, Subhash,Das, Jayanta,Alvarez, Richard P.,Santra, Swadeshmukul
experimental part, p. 302 - 306 (2010/06/13)
A simple and straightforward route for the synthesis of thioethers, thioesters, vinyl thioethers and thio-Michael adducts has been demonstrated using silica nanoparticles (NPs) as a reusable catalyst via the 1,2-addition of thiols to alkenes, alkynes and alkyl/acyl halides, and the 1,4-addition of thiols to conjugated alkenes at room temperature.
Reactions of 2-(α-Haloalkyl)thiiranes with nucleophilic reagents: V.* Reactions of 2-(α-chloroalkyl)thiiranes with organolithium compounds
Tomashevskii,Sokolov,Potekhin
experimental part, p. 1822 - 1825 (2011/04/17)
2-(α-Haloalkyl)thiiranes reacted with methyl-, butyl-, and phenyllithium to give the corresponding allyl sulfides. The reactions of diastereoisomeric erythro-and threo-2-(1-chloroethyl)thiiranes with phenyllithium were stereospecific, and they afforded (E)-and (Z)-1-phenylsulfanylbut-2-enes, respectively. 3-Chloromethyl-2,2- dimethylthiirane and phenyllithium gave rise to a mixture of 3-methyl-3-phenylsulfanylbut-1-ene and 3-methyl-1-phenylsulfanylbut-2-ene. The reactions of 2-chloromethylthiiranes with phenyllithium and methyllithium in the presence of a catalytic amount of copper(I) iodide (10 mol %) led to the formation of substituted thiiranes as the major products. Mechanisms of the observed transformations are discussed. Pleiades Publishing, Ltd., 2010.
Phosphorus functionalized dendrimers and hyperbranched polymers: Is there a need for perfect dendrimers in catalysis?
Ribaudo, Fabrizio,Van Leeuwen, Piet,Reek, Joost
experimental part, p. 79 - 98 (2010/03/03)
In this paper we describe the facile and straightforward covalent functionalization of commercially available dendritic poly(propylenimine) and hyperbranched poly(ethylenimine) with P-containing functional groups. The P-functionalized macromolecules have been applied as multivalent ligands in the Pd-catalyzed allylic substitution reactions (batch and continuous process) using either morpholine or thiophenol as nucleophile. Palladium complexes of all described molecules are active in allylic substitution reactions. The PEI functionalized polymers appear more sensitive to small changes in the P/Pd ratio than the PPI analogues, but form catalysts that are more active. When used in a continuous flow process the macromolecules are completely retained by the nanofiltration membrane, while the catalytic activity decreases with time because of palladium depletion. This is more severe for the allylic thiolation, probably because of the stronger affinity of sulfur for palladium, facilitating palladium leaching.
Ionic liquid as catalyst and reaction medium: A simple, convenient and green procedure for the synthesis of thioethers, thioesters and dithianes using an inexpensive ionic liquid, [pmIm]Br
Ranu, Brindaban C.,Jana, Ranjan
, p. 1811 - 1818 (2007/10/03)
An easily accessible and inexpensive room temperature ionic liquid, 1-pentyl-3-methylimidazolium bromide, [pmIm]Br efficiently catalyzes the reaction of alkyl halides or acyl halides with thiols without any solvent at room temperature leading to the synthesis of thioethers and thioesters in high yields. This reaction has also been extended for the preparation of dithianes and transthioetherification. The ionic liquid is recovered and recycled for subsequent runs.
Selective allylation of arenethiols using water-soluble palladium complex catalyst in recyclable water/hexane biphasic media
Komine, Nobuyuki,Sako, Akari,Hirahara, Shin-Ya,Hirano, Masafumi,Komiya, Sanshiro
, p. 246 - 247 (2007/10/03)
Allylation of arenethiols by allylic alcohol with sterically hindered carbon of the allylic moiety is smoothly catalyzed by Pd(OAc)2/TPPTS in biphasic water/hexane media under ambient conditions. The catalyst water layer can be repeatedly reuse
A mild and highly convenient chemoselective alkylation of thiols using Cs2CO3-TBAI
Salvatore, Ralph Nicholas,Smith, Robert A.,Nischwitz, Adam K.,Gavin, Terrence
, p. 8931 - 8935 (2007/10/03)
A mild and improved method for the synthesis of thioethers has been developed. In the presence of cesium carbonate, tetrabutylammonium iodide, and DMF, various alkyl and aryl thiols underwent S-alkylation to afford structurally diverse sulfides in high yield. Unprotected mercaptoalcohols and thioamines reacted chemoselectively at the sulfur moiety exclusively. An example of a one-pot, solid-phase synthesis of a thioether is also described.
Aromatic Allylsulfenylation with in Situ Generated Allylic Thiols under the Heck Conditions
Harayama, Hiroto,Nagahama, Takayuki,Kozera, Toyohiro,Kimura, Masanari,Fugami, Keigo,Tanaka, Shuji,Tamaru, Yoshinao
, p. 445 - 456 (2007/10/03)
A wide structural variety of S-allylic thiocarbamates 2 can be prepared in good yields by the rearrangement of O-allylic thiocarbamates 1 under three different conditions: thermal activation (neat, 120-150°C), palladium(0) (25-65 °C), and palladium(II) catalysis (25-65°C). Of the two possible regioisomers of unsymmetrical S-allylic thiocarbamates 2, those of higher thermodynamic stability can be prepared in high purity under either thermal activation or palladium(0) catalysis. Although the thermodynamically less stable regioisomers of 2 are, in general, hard to be prepared in high purity, some of them (e.g., 2d and 2h′) can be obtained with an exclusive or high selectivity by the catalysis of palladium(II). The stereoisomeric pair of 2j and 2j′ can be prepared selectively by the palladium(0)-catalyzed rearrangement of 1j and 1k, respectively. These reactions proceed with retention of configuration at the allylic stereocenters, S-Allylic (2) and S-alkyl thiocarbamates (7) undergo fragmentation to generate thiolates in the presence of inorganic bases (e.g., K2CO3, K2CO3·-Et4N+I-) by heating in an aprotic solvent; the thus-formed thiolates react with aromatic iodides and vinyl bromides in the presence of palladium(0) complexes to furnish aryl and vinyl sulfides, respectively. A wide variety of aryl sulfides can be prepared in good yields irrespective of the kind of substituents and their substitution positions (o-, m-, p-) under conditions B [Pd(OAc)2, PPh3, K2CO3·Et4N+I-, dioxane, 100°C]. Under conditions E [Pd(OAc)2, PPh3, Cs2CO3, dioxane, 100°C], better yields result specifically for the sulfenylation of aromatic iodides bearing substituents having large Hammett σ constants.
Aromatic allylsulfenylation with in situ generated allyl thiols under the Heck conditions
Harayama, Hiroto,Kozera, Toyohiro,Kimura, Masanari,Tanaka, Shuji,Tamaru, Yoshinao
, p. 543 - 544 (2007/10/03)
By the catalysis of palladium(0), S-allyl thiocarbamates 1 react with aryl iodides and vinyl bromides to give allyl aryl sulfides and allyl vinyl sulfides, respectively, in good yields.
A 1H and 13C NMR Study of the Structure of Sulfur-Stabilized Lithiated Allylic Carbanions
Glendenning, Lionel,Field, Leslie D.,Haynes, Richard K.
, p. 2739 - 2750 (2007/10/03)
NMR studies of the solution structures of lithiated (E)-1-(t-butylthio)but-2-ene (4) and lithiated (E)-1-(phenylthio)but-2-ene (6) are reported.The structure of lithiated (E)-1-(t-butylthio)but-2-ene (4) is best described as a transoid carbanion with the allylic carbons C1, C2, and C3 having intermediate sp2-sp3 hybridization.In (4) the heteroatom and non-allylic substituent do not play any significant role in carbanion stabilization.Lithiated (E)-1-(phenylthio)but-2-ene (6) differs from (4) in that it exhibits cis geometry about the C1-C2 bond and the phenylthio group participates in helping to stabilize allylic charge.There is a discrepancy between the geometry about the C1-C2 bond in the solution and solid structures of (4) in the presence of TMEDA.
