56772-75-9Relevant articles and documents
Straightforward chemoselective access to unsymmetrical dithioacetals through a thiosulfonate homologation-nucleophilic substitution sequence
Ielo, Laura,Pillari, Veronica,Gajic, Natalie,Holzer, Wolfgang,Pace, Vittorio
supporting information, p. 12395 - 12398 (2020/10/30)
A sequential C1-homologation-nucleophilic substitution tactic is presented for the preparation of rare unsymmetrical dithioacetals. The judicious selection of thiosulfonates as convenient sulfur electrophilic sources - upon the homologation event conducted on an intermediate a-halothioether - guarantees the release of the non-reactive sulfonate group, thus enabling the subsequent nucleophilic displacement with an external added thiol [(hetero)- aromatic and/or aliphatic]. Uniform high yields and excellent chemocontrol were deduced during the extensive scope study, thus documenting the versatility of the direct technique for the preparation of these unique and manipulable materials.
Synthesis and novel reactivity of halomethyldimethylsulfonium salts
Xu, Yuelian,Fletcher, Michelle,Dolbier Jr., William R.
, p. 3460 - 3465 (2007/10/03)
Iodomethyl-, chloromethyl-, and fluoromethyldimethylsulfonium salts, 4b-d, have been synthesized and are observed to be highly reactive molecules that exhibit extraordinary diversity with respect to the nature of their reactivity, undergoing facile direct substitution (SN2) reactions, but also being highly susceptible to electron-transfer reactions. Cyclic voltametry experiments indicated that the iodomethyldimethylsulfonium compound, 4b, is a potent electron acceptor, even surpassing the reactivity of perfluoro-n-alkyl iodides in that capacity. The iodo- and chloromethyldimethylsulfonium salts, 4b,c, as well as the analogous iodomethyltrimethylammonium salt, 3a, are shown to be reactive SET acceptors.
Reactions of Sulfoxides with Magnesium Amides. Transformations of Sulfoxides into Sulfides, Dithioacetals and Vinyl Sulfides
Kobayashi, Kazuhiro,Kawakita, Masataka,Yokota, Kouichi,Mannami, Tohru,Yamamoto, Koji,et al.
, p. 1401 - 1408 (2007/10/02)
The reactions of sulfoxides with magnesium amides generated in situ from the reaction of ethylmagnesium bromide and seconday amines, such as diisopropylamine (DIPA) or 2,2,6,6-tetramethylpiperidine (TMP) in diethyl ether, were examined.Diaryl sulfoxides were heated with the diisopropylaminomagnesium reagent in diethyl ether to give the corresponding diaryl sulfides in 42-52percent yields.Sulfoxides bearing hydrogens at the α-position only(RSOCH2R1) reacted with the tetramethylpiperidinomagnesium reagent at room temperature to produce the corresponding dithioacetals (RSCHR1SR) in 47-86percent yields.The treatment of sulfoxides bearing hydrogens both at the α-and β-positions (RSOCHR1CHR2R3) with the magnesium amides at room temperature afforded the corresponding vinyl sulfides (RSCR1=CR2R3) in 52-72percent yields accompanying 2.3-27percent yields of the corresponding dithioacetals.The pathways leading to the products involving the formation of the sulfur-stabilized carbonium ion intermediates are discussed.
