701-75-7Relevant academic research and scientific papers
Expanding the horizon of intermolecular trapping of in situ generated α-oxo gold carbenes: Efficient oxidative union of allylic sulfides and terminal alkynes via C-C bond formation
Li, Jiabin,Ji, Kegong,Zheng, Renhua,Nelson, Jonathan,Zhang, Liming
supporting information, p. 4130 - 4133 (2014/04/03)
With a new P,S-bidentate phosphine as the ligand to gold(i), the α-oxo gold carbenes generated in situ via gold-catalyzed intermolecular oxidation of terminal alkynes were effectively trapped by various allylic sulfides, resulting in the formation of α-aryl(alkyl)thio-γ,δ- unsaturated ketones upon facile [2,3]sigmatropic rearrangements. This journal is the Partner Organisations 2014.
One-pot reductive sulfenylation and thiocyanation of carbonyl compounds in ionic liquid media
Yadav, Lal Dhar S.,Garima,Kapoor, Ritu
experimental part, p. 100 - 112 (2011/03/17)
The first example of an efficient one-pot reductive sulfenylation and thiocyanation of carbonyl compounds in environmentally benign ionic liquid (IL) media is reported. The process involves reduction of carbonyl compounds with NaBH4 in the IL [bmim]BF4 followed by I2-catalyzed reaction of the resulting alcohols with aromatic/aliphatic thiols or ammonium thiocyanate in the same vessel to afford sulfides or thiocyanates, respectively, in excellent yields (78-93%). Notably, the protocol precludes the necessity to prepare and isolate the intermediate alcohols in a separate step as they are formed in situ, and the IL used can be recycled easily for further use without any loss of efficiency. Copyright
Silylene transfer to allylic sulfides: Formation of substituted silacyclobutanes
Ager, Bryan J.,Bourque, Laura E.,Buchner, Kay M.,Woerpel
supporting information; experimental part, p. 5729 - 5732 (2010/11/04)
Silylene transfer to allylic sulfides results in a formal 1,2-sulfide migration. The rearrangement yields substituted silacyclobutanes, not the expected silacyclopropanes. The silacyclobutanes were elaborated by insertions of carbonyl compounds selectively into one carbon-silicon bond. A mechanism for the 1,2-sulfide migration is proposed involving an episulfonium ion intermediate.
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.
Fast ruthenium-catalysed allylation of thiols by using allyl alcohols as substrates
Zaitsev, Alexey B.,Caldwell, Helen F.,Pregosin, Paul S.,Veiros, Luis F.
scheme or table, p. 6468 - 6477 (2010/02/28)
The allylation of aromatic and aliphatic thiols, by using allyl alcohols as substrates, requires only minutes at ambient temperature with either a Ru Iv catalyst, [Ru(Cp*)(n3CH5)(CH 3CN)2](PF6)2 (2; Cp* = pentamethylcyclopentadienyl) or a combination of [Ru(Cp*)(CH 3CN)3](PF6) and camphor sulfonic acid. Quantitative conversion is normal and the catalyst possesses high functional-group tolerance. The use of [Ru(Cp*)(CH3CN) 3](PF6) alone affords poor results. A comparison is made to the results from catalytic runs based on the use of carbonates rather than alcohols, by using 2 as the catalyst, and it is shown that the products from the alcohols are formed faster, so there is no advantage in using a carbonate substrate. The observed branched-to-linear (b/1) ratios when using substituted alcohols decrease with time suggesting that the catalysts isomerise the products. A new methodology from which one can select the desired isomeric product is proposed. DFT calculations and NMR spectroscopic measurements, by using an arene sulfonic acid as co-catalyst, suggest that 6-complexes are not relevant for the catalytic system. Moreover, the DFT results indicate that l)any rf-complexes from the acids RC6H4SO 3H result from deprotonation of the acid, 2) complexation of the thiol, via the deprotonated sulfur atom, is preferred over complexation of the O atom of the sulfonate, RC6H4SO3and 3) a sulfonate O-atom complex will be difficult to detect.
Mechanical stirring speed in water/hexane biphasic catalyst controls regioselectivity of Pd-catalyzed allylation reaction
Komiya, Sanshiro,Sako, Akari,Kosuge, Hirofumi,Hirano, Masafumi,Komine, Nobuyuki
, p. 640 - 641 (2008/12/21)
Vigorous mechanical mixing of the water/hexane biphasic Pd-catalyzed allylation of benzenethiol gave sterically congested allyl sulfides, due to high reactivity of the enforced orientation of the η1-allylpalladium intermediate at the solvent in
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
Cleavage of Co-C bond in allyl cobaloximes with arenesulphenyl chloride
Gupta,Dixit,Singh,Kanth
, p. 830 - 834 (2007/10/03)
Arenesulphenyl chlorides (ArSCl; Ar = Ph, C6Cl5, 2,4(NO2)2 C6H3) are reacted with allylcobaloximes, RCo(dmgH)2Py (R= allyl), under thermal and photochemical conditions to obtain the corresponding sulphides as the major organic products. α-Pinenyl cobaloxime forms the ring opened product as well. The homolytic as well as heterolytic cleavage of the Co-C bond is considered.
SH2' Type Reactions of Arenesulfonyl Chlorides with Allylic Compounds Catalyzed by a Ruthenium(II) Complex
Kamigata, Nobumasa,Ishii, Kimiko,Ohtsuka, Takeshi,Matsuyama, Haruo
, p. 3479 - 3481 (2007/10/02)
In the presence of a catalytic amount of dichlorotris(triphenylphosphine)ruthenium(II), the reactions of arenesulfonyl chlorides with allyl phenyl sulfide and allyl phenyl selenide proceeded smoothly to give allyl phenyl sulfone in high yield as well as the corresponding diphenyl disulfide or diphenyl diselenide.An SH2'-type mechanism involving the arenesulfonyl radical is proposed.
