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- Title
Mechanistic Insights for Dimethyl Sulfoxide Catalyzed Aromatic Chlorination Reactions.
- Authors
Qu, Zheng‐Wang; Zhu, Hui; Grimme, Stefan
- Abstract
Recently, the dimethyl sulfoxide O=SMe2 catalyzed aromatic chlorination reaction using N‐chlorosuccinimides (NsCl) under mild conditions has proven useful for bioactive compounds potentially containing various functional groups such as amide and hydroxyl. A novel catalytic mechanism is revealed by extensive DFT calculations using the anisole PhOMe as electron‐rich model substrate. The Cl+ transfer from NsCl to O=SMe2 slowly reacts via the S‐chloro sulfoxonium O=SClMe2+ to the S‐chloro ylide O=SClMeCH2, followed by facile Cl+ transfer from NsCl to the ylide CH2 site to initialize efficient electrophilic Cl+ transfer to nucleophilic substrates. According to the new proposal, the polarizable S and electronegative O sites of O=SMe2 may act as efficient Cl+ and H+ shuttles, respectively, in catalytic aromatic chlorination. If O=SMe2 is present in high concentration, it can trap intermediate SMe2OH+ into a stable H+‐bound dimer (SMe2O)2H+ to inhibit efficient protic NsCl activation. These mechanistic insights may be generally useful for the rational design of novel dual functional halonium transfer catalysts.
- Subjects
CHLORINATION; HYDROXYL group; AMIDES; ANISOLE; BIOACTIVE compounds; FUNCTIONAL groups; WATER chlorination; DIMETHYL sulfoxide
- Publication
ChemCatChem, 2021, Vol 13, Issue 1, p207
- ISSN
1867-3880
- Publication type
Article
- DOI
10.1002/cctc.202001396