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Finds direct neutral synthesis of thioethers in DMF, suggesting a greener synthetic approach.
Different to other solvents, a unique promoting effect of DMF is observed in the aromatic nucleophilic substitution reaction of heteroaryl halides and thiols. Thus, by using DMF as the solvent, a greener method can be developed for direct neutral synthesis of heteroaryl thioethers without adding any external base into the reaction. This method can also be extended to alkyl and electron‐deficient aryl halides, providing a new way for external base‐free neutral construction of the useful unsymmetrical thioethers. Control reactions revealed that DMF functions more than a good solvent in the reaction, i.e., a synergetic bifunctional effect of DMF working as both the best solvent and an excellent organic base can eventually promote the substitution reactions of thiols and organohalides effectively without using any external base.
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Li et al. (2026) studied this question.
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