Palladium-catalyzed allylation reactions of 2-(chloromethyl)thiophenes, 2-(chloromethyl)furans, and N-protected 2-(chloromethyl)-1H-pyrroles with allyltributylstannane were described in this study. This type of allylation reaction regioselectively occurred on the heteroarene rings to produce allylated dearomatization products or allylated heteroarenes with satisfactory yields.

The synthesis of thiazoles and thiophenes starting from nitriles, via a modified Gewald reaction has been studied for a number of different substrates. 1,4-Dithiane-2,5-diol was used as the aldehyde precursor to give either 2-substituted thiazoles or 2-substituted aminothiophenes depending on the substitution of the α-carbon to the cyano group.

The facile and clean oxidative biaryl coupling reaction of thiophenes and pyrroles has been achieved using the recyclable hypervalent iodine(III) reagents having adamantane or methane structures. These iodine(III) reagents could be recovered from the reaction mixtures by a simple solid-liquid separation, i.e., filtration.

Reaction of bis(tert-butylethynyl)sulfide with the boron Lewis acid reagents X-B(C6F5)2 (X = CH3, Cl, C6F5) in pentane at r.t. gave the respective borylated thiophenes in a sequence of 1,1-carboboration reactions. In contrast, bis(phenylethynyl)sulfide reacted with B(C6F5)3 only in a 2 : 1 molar ratio to give a benzothiophene derivative.

A Ni-catalyzed asymmetric reductive cross-coupling of heteroaryl iodides and α-chloronitriles has been developed. This method furnishes enantioenriched α,α-disubstituted nitriles from simple organohalide building blocks. The reaction tolerates a variety of heterocyclic coupling partners, including pyridines, pyrimidines, quinolines, thiophenes, and piperidines. The reaction proceeds under mild ...

Three-component couplings were achieved from common aryl halides, alkyl halides, and heteroarenes under palladium and norbornene co-catalysis. The reaction forges hindered aryl-heteroaryl bonds and introduces ortho-alkyl groups to aryl rings. Various heterocycles such as oxazoles, thiazoles and thiophenes underwent efficient coupling. The heteroarenes were deprotonated in situ by bases without ...

A three-step synthesis of benzo[c]thiophenes is presented in which the key transformation is the gold-catalyzed 5-exo-dig migratory cycloisomerization of a diallyl thioacetal. It was shown that a small amount of in situ generated HAuCl4 from AuCl3 is the active catalytic species. A mechanism was proposed.

An intramolecular cyclization of 2-(gem-dibromovinyl)phenols(thiophenols) to give 2-bromobenzofurans(thiophenes) in the presence of a trace amount of Cu (0.0064 mol%, 25 ppm) has been developed. The reaction provides the desired products in excellent yields under fluoride-free and mild reaction conditions and with a TON (turnover number) of up to 1.5 × 10(4).