Synthesis of benzo[b]furans from alkynyl sulfoxides and phenols by the interrupted Pummerer reaction.

The interrupted Pummerer reaction of alkynyl sulfoxides with phenols is disclosed. A wide range of benzo[b]furans were efficiently synthesized through unexplored electrophilic activation of the electron-deficient alkynyl sulfinyl group. Based on the good availability of alkynyl sulfoxides, we successfully prepared various functionalized benzo[b]furans from readily available alkynes, thiosulfonates, and phenols.

Transition-Metal-Free Synthesis of N-Arylphenothiazines through an N- and S-Arylation Sequence.

An efficient synthetic method of N-arylphenothiazines from o-sulfanylanilines under transition-metal-free conditions is disclosed. An N- and S-arylation sequence of o-sulfanylanilines enabled us to synthesize a wide variety of N-arylphenothiazines. In particular, one-pot synthesis of N-arylphenothiazines was accomplished from easily available modules through preparation of o-sulfanylanilines by thioamination of aryne intermediates and following N- and S-arylation sequence.

Sulfoxide synthesis from sulfinate esters under Pummerer-like conditions.

A facile synthetic method for the preparation of allyl sulfoxides by S-allylation of sulfinate esters proceeds through sulfonium intermediates without [3,3]-sigmatropic rearrangement and further Pummerer-type reactions of the resulting allyl sulfoxides. On the basis of the plausible reaction mechanism involving sulfonium salt intermediates, S-alkynylation and S-arylation were also accomplished.

Synthesis of Diverse Aromatic Ketones through C-F Cleavage of Trifluoromethyl Group.

An efficient synthetic method of aromatic ketones through C-F cleavage of trifluoromethyl group is disclosed. The high functional group tolerance of the transformation and the remarkable stability of trifluoromethyl group in various reactions enabled multi-substituted aromatic ketone synthesis in an efficient route involving useful transformations such as ortho-lithiation, aryne chemistry, and cross-couplings.

One-step synthesis of benzo[b]thiophenes by aryne reaction with alkynyl sulfides.

An aryne reaction with alkynyl sulfides affording benzo[b]thiophenes is disclosed. A wide range of 3-substituted benzothiophenes were synthesized from easily available o-silylaryl triflates and alkynyl sulfides in a one-step intermolecular manner. The synthesis of diverse multisubstituted benzothiophene derivatives involving a pentacyclic compound was achieved by virtue of the good functional group tolerance and versatile C2 functionalizations.

Expanding the synthesizable multisubstituted benzo[b]thiophenes via 6,7-thienobenzynes generated from o-silylaryl triflate-type precursors.

Various 2,3-disubstituted 6,7-thienobenzynes have been efficiently generated from the corresponding o-silylaryl triflate-type precursors by activation with fluoride ions. The method has expanded the scope of synthesizable multisubstituted benzothiophenes, including those with various heteroatom substituents, and can be applied to the synthesis of EP4 antagonist analogs.

Synthesis of Diverse o-Arylthio-Substituted Diaryl Ethers by Direct Oxythiolation of Arynes with Diaryl Sulfoxides Involving Migratory O-Arylation.

A diverse range of o-arylthio-substituted diaryl ethers has been synthesized by direct oxythiolation of arynes with diaryl sulfoxides that involves the formation of the C-O and C-S bonds followed by migratory O-arylation.