A new one-pot strategy for the synthesis of quinoxalin-2-ones from the tandem nitrosation/cyclization reaction of N-aryl cyanoacetamides with tert-butyl nitrite has been developed. The dehydrogenative N-incorporation is achieved through a sequence of nitrosation, tautomerization, and cyclization, affording quinoxalin-2-ones in moderate to good yields with good functional group tolerance.

A new one-pot strategy for the synthesis of quinoxalin-2-ones from the tandem nitrosation/cyclization reaction of N-aryl cyanoacetamides with tert-butyl nitrite has been developed. The dehydrogenative N-incorporation is achieved through a sequence of nitrosation, tautomerization, and cyclization, affording quinoxalin-2-ones in moderate to good yields with good functional group tolerance.

A new transition-metal-free transformation of trifluoropropanamides into cyanoformamides through a sequence of C–CF3 bond cleavage and nitrogenation using tert-butyl nitrite as the nitrogen source is described. The method features direct detrifluoromethylation, broad substrate scopes, and excellent selectivity control, representing a new shortcut for constructing the nitrile group involving C–CF3 σ-bond cleavage.

AbstractA new method for the synthesis of β-iodoalkenyl sulfides via copper catalyzed difunctionalization of styrenes is described. The method allows the formation of two chemical bonds, a C—I bond and a C—S bond, in a single reaction. Using alkenes in place of alkynes to synthesize β-iodoalkenyl sulfides is a significant advantage of this methodology for both synthetic and medicinal chemistry.

A copper-catalyzed three-component tandem reaction has been developed for the convenient and practical synthesis of 1,4-benzothiazines. A variety of terminal alkynes and 2-iodo/bromophenyl isothiocyanates underwent this one-pot cyclization with aqueous ammonia to afford 1,4-benzothiazines in moderate to good yields.

A silver-mediated cascade trifluoromethylthiolation and cyclization has been developed for the synthesis of 2-(trifluoromethylthio)-indenones. A variety of arylpropynones underwent this radical oxidative cyclization with AgSCF3 to afford trifluoromethylthiolated indenones in moderate to excellent yields.

A tandem annulation of arylpropynols with disulfides has been developed for the synthesis of 2-sulfenylindenone derivatives. The reaction pathway involves one-pot tandem Meyer–Schuster rearrangement of arylpropynols and successive radical cyclization with disulfides. Various arylpropynols and disulfides with a number of functional groups are compatible in this reaction that affords the corresponding 2-sulfenylindenones in moderate to good yields.

A copper and iodine-mediated C–H oxidative sulfenylation of olefins with diaryl disulfides has been developed for the stereospecific synthesis of vinyl thioether. With the combination of Cu(OTf)2 and I2, a variety of terminal alkenes underwent oxidative coupling reaction with various diaryl disulfides successfully to afford the corresponding E-vinyl sulfides in moderate to good yields.

A new palladium-catalyzed oxidative carbamoylation reaction of isoquinoline N-oxides with formylamides for the synthesis of isoquinoline-1-carboxamides is established. The method represents the first example of the carbamoylation of isoquinoline N-oxides with formylamides to furnish arylamides using the dual C–H oxidation strategy.

A new ring expansion of 2-aminobenzothiazoles with alkynyl carboxylic acids was developed, which allows for one-pot synthesis of 1,4-benzothiazines in moderate to excellent yields. The cascade reaction was achieved through decarboxylative coupling, nucleophilic ring-opening reaction and intramolecular hydroamination process.

The palladium-catalyzed direct sulfenylation of arenes with N-arylthiobenzamides was developed for the synthesis of aryl sulfides. Additional oxidant was not required for the catalytic cycle because N-arylthiobenzamide was used as both thiolation reagent and oxidant. The selective mono- or di-sulfenylation could be controlled by addition of the amount of N-arylthiobenzamide. Excellent functional group tolerance was observed and thioethers or dithioethers were obtained in good yields.

A novel one-pot strategy for the synthesis of 3-trifluoromethylquinoxalines from N-aryl enamines and nitromethane was developed. The tandem reaction is achieved through nitrosation of alkenes, tautomerization and cyclization, which can be applicable to a wide range of enamines with excellent functional group tolerance and afford quinoxalines in moderate to good yields.

A two-step, one-pot tandem iodocyclization and trifluoromethylation have been developed. A variety of 3-trifluoromethylbenzofurans were prepared in moderate to good yields via the tandem reaction of 2-alkynylanisoles with elemental iodine and (trifluoromethyl)trimethylsilane.

An iron-promoted tandem carboxamidation and cyclization between aryl isonitriles and formamides has been developed. The one-pot strategy can be applied to a wide range of 2-isocyanobiphenyls and formamides with excellent functional group tolerance for the synthesis of phenanthridine-6-carboxamides in moderate to excellent yields.

A palladium-catalyzed tandem Suzuki/C–H arylation reaction of N-aryltrifluoroacetimidoyl chlorides with arylboronic acids has been developed. A variety of 6-(trifluoromethyl)phenanthridines were prepared in moderate to excellent yields from N-(2-bromophenyl)trifluoroacetimidoyl chlorides which can be conveniently prepared from 2-bromoaniline derivatives.

A palladium-catalyzed, iodine-mediated electrophilic annulation between 2-(1-alkynyl)biphenyl and disulfide has been developed. With the combination of PdCl2 and I2, a variety of 2-(1-alkynyl)biphenyls underwent electrophilic annulations with various disulfides successfully to afford the corresponding 9-sulfenyl phenanthrenes in moderate to excellent yields.

A palladium- and copper-catalyzed tandem N–H/C–H bond functionalization reaction of ortho-(2-chlorovinyl)bromobenzenes with indoles and pyrroles has been developed. A variety of CF3-containing indolo- and pyrrolo[2,1-a]isoquinolines were prepared in moderate to good yields via the cyclization of 1-bromo-2-(2-chloro-3,3,3-trifluoroprop-1-enyl)benzenes with indoles and pyrroles.

A copper-catalyzed thiolation annulation reaction of 2-bromo alkynylbenzenes with sodium sulfide has been developed. In the presence of CuI and TMEDA, a variety of 2-substituted benzo[b]thiophenes were readily prepared in moderate to good yields by the reaction of 2-bromo alkynylbenzenes and Na2S·9H2O.

A highly efficient Suzuki reaction between N-aryltrifluoroacetimidoyl chlorides and aryl boronic acids using Pd(PPh3)4 as a catalyst has been developed. This route allows for selective synthesis of N-aryl trifluoromethylarylketoimines in high yields under mild reaction conditions.A highly efficient synthesis of N-aryl trifluoromethylarylketoimines by palladium-catalyzed Suzuki coupling reaction between N-aryltrifluoroacetimidoyl chlorides and aryl boronic acids is described.

A new type of iodo-containing trifluoromethylated building blocks were synthesized. The reaction of 1-aryl-3,3,3-trifluoropropynes 1 with lithium iodide in acetic acid at 75 °C gave (E)-1-aryl-3,3,3-trifluoro-1-iodo-propenes 2 in high yield, which undergo the palladium-catalyzed Sonogashira reaction with terminal alkynes afforded trifluoromethyl-containing 1,3-enynes in high yield.

A new palladium-catalyzed oxidative carbamoylation reaction of isoquinoline N-oxides with formylamides for the synthesis of isoquinoline-1-carboxamides is established. The method represents the first example of the carbamoylation of isoquinoline N-oxides with formylamides to furnish arylamides using the dual C–H oxidation strategy.

A new ring expansion of 2-aminobenzothiazoles with alkynyl carboxylic acids was developed, which allows for one-pot synthesis of 1,4-benzothiazines in moderate to excellent yields. The cascade reaction was achieved through decarboxylative coupling, nucleophilic ring-opening reaction and intramolecular hydroamination process.

A copper and iodine-mediated C–H oxidative sulfenylation of olefins with diaryl disulfides has been developed for the stereospecific synthesis of vinyl thioether. With the combination of Cu(OTf)2 and I2, a variety of terminal alkenes underwent oxidative coupling reaction with various diaryl disulfides successfully to afford the corresponding E-vinyl sulfides in moderate to good yields.

A novel one-pot strategy for the synthesis of 3-trifluoromethylquinoxalines from N-aryl enamines and nitromethane was developed. The tandem reaction is achieved through nitrosation of alkenes, tautomerization and cyclization, which can be applicable to a wide range of enamines with excellent functional group tolerance and afford quinoxalines in moderate to good yields.