830-72-8Relevant articles and documents
Reactions of thioketones with a fluorinated thione S-imide
Mloston, Grzegorz,Celeda, Malgorzata,Roesky, Herbert W.,Parisini, Emilio,Ahlemann, Jens-Thomas
, p. 459 - 465 (1998)
N-(1-Adamantyl)hexafluorothioacetone S-imide (1) reacts readily with aromatic thioketones 4a-e to afford 1,4,2-dithiazolidines 5a-e as products of [3 + 2] dipolar cycloadditions. Unexpectedly, cycloadducts 5d and 5e, obtained from thioxanthione (4d) and 4,4′-(dimethoxy)thiobenzophenone (4e), respectively, are found to decompose at room temperature and could not be isolated as pure compounds. Unlike aromatic thiones, adamantanethione (4f) did not react with 1 at ambient temperature. However, reaction did occur upon heating in a sealed tube, and the new 1,4,2-dithiazolidine 9, bearing two adamantyl moieties, was isolated as the major product. The structure of 9 has been determined by X-ray diffraction analysis. The connectivity of the heterocyclic ring in this product indicates that the mechanism of its formation must proceed by a different route involving another in situ generated sulfur-centered 1,3-dipole. Retrocycloaddition of the primary adamantanethione cycloadduct 13 liberates hexafluorothioacetone, which is subsequently captured by Simide 1 to give tetrakis(trifluoromethyl)-1,4,2-dithiazolidine 8 as a crystalline product. The structure of 8 has also been confirmed by X-ray diffraction analysis.
New procedure for the preparation of highly sterically hindered alkenes using a hypervalent iodine reagent
Ter Wiel, Matthijs K. J.,Vicario, Javier,Davey, Stephen G.,Meetsma, Auke,Feringa, Ben L.
, p. 28 - 30 (2005)
A method to construct the olefinic bond in overcrowded alkenes using hypervalent iodine reagent was discussed. In the process, the diazo compound was made to react in a 1,3-dipolar cycloaddition with thioketone to form two isomeric thiadiazolines, which were unstable. A single isomer of episulfide was formed, since the methyl substituent blocks ring closure on one side of the molecule of the essentially flat thiocarbonyl yielded moiety. The method is very efficient because it allows selective coupling reaction and facilitates purification of the desired product.
One-Pot Catalytic Cleavage of C=S Double Bonds by Pd Catalysts at Room Temperature
Zhu, Ting,Wu, Xiaoxi,Yang, Xinzheng,Sharma, Bigyan,Li, Na,Huang, Jiaming,Wang, Wentao,Xing, Wang,Zhao, Zhenwen,Huang, Hui
supporting information, p. 9266 - 9273 (2018/08/17)
The C=S double bonds in CS2 and thioketones were catalytically cleaved by Pd dimeric complexes [(N∧N)2Pd2(NO3)2](NO3)2 (N∧N, 2,2′-bipyridine, 4,4′-dimethylbipyridine or 4,4′-bis(trifluoromethyl)) at room temperature in one pot to afford CO2 and ketones, respectively, for the first time. The mechanisms were fully investigated by kinetic NMR, isotope-labeled experiments, in situ ESI-MS, and DFT calculations. The reaction is involved a hydrolytic desulfurization process to generate C=O double bonds and a trinuclear cluster, which plays a pivotal role in the catalytic cycle to regenerate the dimeric catalysts with HNO3. Furthermore, the electronic properties of catalyst ligands possess significant influence on reaction rates and kinetic parameters. At the same temperature, the reaction rate is consistent with the order of electronegativity of N∧N ligands (4,4′-bis(trifluoromethyl) > 2,2′-bipyridine > 4,4′-dimethylbipyridine). This homogeneous catalytic reaction features mild conditions, a broad substrate scope, and operational simplicity, affording insight into the mechanism of catalytic activation of carbon sulfur bonds.
Bifunctional Molecular Photoswitches Based on Overcrowded Alkenes for Dynamic Control of Catalytic Activity in Michael Addition Reactions
Pizzolato, Stefano F.,Collins, Beatrice S. L.,van Leeuwen, Thomas,Feringa, Ben L.
supporting information, p. 6174 - 6184 (2017/05/05)
The emerging field of artificial photoswitchable catalysis has recently shown striking examples of functional light-responsive systems allowing for dynamic control of activity and selectivity in organocatalysis and metal-catalysed transformations. While o
