Desulfurative Chlorination of Alkyl Phenyl Sulfides

Abstract

The chlorination of readily available secondary and tertiary alkyl phenyl sulfides using (dichloroiodo)benzene (PhICl) is reported. This mild and rapid nucleophilic chlorination is extended to sulfa-Michael derived sulfides, affording elimination-sensitive β-chloro carbonyl and nitro compounds in good yields. The chlorination of enantioenriched benzylic sulfides to the corresponding inverted chlorides proceeds with high stereospecificity, thus providing a formal entry into enantioenriched chloro-Michael adducts. A mechanism implying the formation of a dichloro-λ-sulfurane intermediate is proposed.

Visible‐Light‐Driven Iron‐Promoted Thiocarboxylation of Styrenes and Acrylates with CO2

“…Finally, a gram‐scale reaction was carried out to demonstrate easy scalability (Scheme a). The importance and utility of this method was validated by transformations of 3 ab to γ‐sulfide alcohol 4, esters 5 and 6 , and bioactive compounds and drugs, including β‐sulfonylhydroxamic acid derivative 7 , 1‐thioflavanone ( 8 ), and thiazensim ( 9 )…”

Synergistic Cooperative Effect of L‐Arginine‐[bmim]Br in Cascade Decarboxylative Knoevenagel‐Thia‐Michael Addition Reactions: Green Approach Towards C−S Bond Formation with In Situ Generated Unactivated α,β‐Unsaturated Ester

“…Ethyl 3‐(4‐chlorophenyl)‐3‐(phenylthio)propanoate [5 e] . 73% yield (83 mg), colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.33–7.29 (m, 2H), 7.29–7.23 (m, 5H), 7.21–7.17 (m, 2H), 4.62 (dd, J =8.7, 6.9 Hz, 1H), 4.07 (dd, J =7.1, 4.0 Hz, 2H), 2.92 (qd, J =15.8, 7.8 Hz, 2H), 1.18 (t, J =7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ170.43, 139.18, 133.56, 133.18, 133.15, 129.01, 128.92, 128.56, 128.03, 60.79, 48.57, 40.83, 14.07.…”

Intermolecular Pummerer Coupling with Carbon Nucleophiles in Non‐Electrophilic Media

“…Marek's methylenation furnishes 10 , which can produce epoxides, aziridines, and cross‐metathesis products. Alkyl halides like the chloride 11 and the fluoride 12 can be obtained (the latter through a new nickel‐promoted reaction that we are currently studying). The reductive lithiation pioneered by Screttas,, provides access to C(sp 3 )‐hybridized organolithiums which can produce, for example, aldehydes and boronic esters for downstream manipulations (i.e., 13 , 14 )…”