18715-44-1Relevant articles and documents
Making the SF5 Group More Accessible: A Gas-Reagent-Free Approach to Aryl Tetrafluoro-λ6-sulfanyl Chlorides
Pitts, Cody Ross,Bornemann, Dustin,Liebing, Phil,Santschi, Nico,Togni, Antonio
supporting information, p. 1950 - 1954 (2019/01/25)
Modern pentafluorosulfanyl (SF5) chemistry has an Achilles heel: synthetic accessibility. Herein, we present the first approach to aryl-SF4Cl compounds (key intermediates in state-of-the-art aryl-SF5 synthesis) that overco
Preparation of difluoromethylthioethers through difluoromethylation of disulfides using TMS-CF2H
Howard, Joseph L.,Schotten, Christiane,Alston, Stephen T.,Browne, Duncan L.
supporting information, p. 8448 - 8451 (2016/07/07)
We report an operationally simple, metal-free approach for the late-stage introduction of the important lipophilic hydrogen-bond donor motif, SCF2H. This reaction converts diaryl- and dialkyl-disulfides into the corresponding aryl/alkyl-SCF2H through the nucleophilic transfer of a difluoromethyl group with good functional group tolerance. This method is notable for its use of commercially available TMSCF2H, and does not rely on the need for handling of sensitive metal complexes.
Vinyl Selenides and Selenoxides: Preparation, Conversion to Lithium Reagents, Diels-Alder Reactivity, and Some Comparisons with Sulfur Analogues
Reich, Hans J.,Willis, William W.,Clark, Peter D.
, p. 2775 - 2784 (2007/10/02)
A variety of aryl vinyl selenides are prepared by reaction of vinyl Grignard reagents with aryl selenyl bromides or by reductive elimination of the adducts of lithiums with carbonyl compounds.Deprotonation of phenyl vinyl selenide is achieved with LDA at -78 deg C in THF.Vinyl selenides with β-alkyl groups require LiTMP and warmer temperatures (-50 deg C) for complete deprotonation.Allylic lithium reagents were obtained from 1-propenyl and 2-methyl-1-propenyl selenides whereas 1-butenyl or 3-methyl-1-butenyl selenides gave vinyl lithium reagents.Reaction with electrophiles proceeds in good to excellent yield.Primary halides require HMPA to react well.Unhindered carbonyl compounds react without enolization.Deprotonation with LDA is shown to be reversible, and during competitive deprotonation studies with LDA, aryl vinyl sulfides are found to be thermodynamically less acidic than aryl vinyl selenides (KS/Se=0.21 for phenyl vinyl and 0.3 for m-(trifluoromethyl)phenyl vinyl).Deprotonation with LiTMP is shown to be irreversible, and competitive deprotonation studies showed vinyl selenide to be kinetically more acidic as well S/Se=0.37 (phenyl vinyl),0.42 (m-(trifluoromethyl)phenyl vinyl)>.Most studies have shown sulfur compounds to be more acidic. m-(Trifluoromethyl)phenyl allyl sulfide as expected, is more acidic than selenium compound (kS/Se=3.8).Vinyl selenoxides can be prepared with m-chloroperbenzoic acid.They are not thermally stable enough to serve as acetylene equivalents in Diels-Alder reactions.Phenyl vinyl selenide gives a Diels-Alder addition product with 1,4-diphenylisobenzofuran but failed to give cycloaddition products with less reactive dienes.Phenyl vinyl selenoxide does not give a useful yield of lithium reagent upon reaction with amide bases.
