The trifluoromethylthio group （SCF3） is a fluorine chemotype that has experienced a strong acceleration of in- terest in the recent years. It is particularly true of the construction of new fluorinated architectures...The trifluoromethylthio group （SCF3） is a fluorine chemotype that has experienced a strong acceleration of in- terest in the recent years. It is particularly true of the construction of new fluorinated architectures by electrophilic trifluoromethylthiolation. The spread of knowledge was already very active in this research domain in the sixties; however, gaseous and highly toxic trifluoromethanesulfenyl chloride （CF3SC1） was the only reagent available at that time. Nowadays, one really can speak of a revival in the field thanks to the rapid development of a wide pano- ply of reagents that are stable and easy to handle. This review provides a historical perspective of the development of shelf-stable electrophilic trifluoromethylthiolation reagents.展开更多
Lewis base catalyzed and Brønsted acid controlled chemodivergent electrophilic selenofunctionalizations of alkynes were developed for the first time.Various selenium-containing tetrasubstituted alkenes were readi...Lewis base catalyzed and Brønsted acid controlled chemodivergent electrophilic selenofunctionalizations of alkynes were developed for the first time.Various selenium-containing tetrasubstituted alkenes were readily obtained in moderate to excellent yields with complete E/Z selectivities.As the substrates were 1-ethynyl naphthol derivatives,linear selenium-containing tetrasubstituted alkenes were produced via intermolecular oxygen nucleophilic attack in the absence of acid additive;in contrast,cyclic selenium-containing tetrasubstituted alkenes were generated through intramolecular carbon nucleophilic capture with the addition of Brønsted acid.展开更多
Two novel compounds,3,8-dibromo-2-methoxyl-7-isopropoxyisoflavanone (1) and 3,6-dibromo-2-methoxyl-7-isopropoxyisoflavanone (2),are synthesized via bromination reaction of their precursor ipriflavone in methanol.The m...Two novel compounds,3,8-dibromo-2-methoxyl-7-isopropoxyisoflavanone (1) and 3,6-dibromo-2-methoxyl-7-isopropoxyisoflavanone (2),are synthesized via bromination reaction of their precursor ipriflavone in methanol.The mixture of 1 and 2 co-crystallizes in ethanol and forms two different crystal shapes,the shape of 1 being block and 2 prism,they can be separated manually.1 and 2 are characterized by IR,1H NMR and single crystal X-ray diffraction.The mechanism of bromination reaction is also discussed.1 crystallizes in the monoclinic space group P 21/n with cell parameters a = 1.3569(3) nm,b = 0.6706(2) nm,c = 2.0704(4) nm,?= 97.50(2)°,V = 1.8678(6) nm3,Z = 4,Dc = 1.672 Mg/m3,R = 0.0455,wR = 0.0779,F(000) = 936.2 crystallizes in the monoclinic space group P 21/c with cell parameters a =1.3854(17) nm,b = 1.1215(14) nm,c = 1.3038(17) nm,? = 103.71(2)°,V = 1.968(4) nm3,Z = 4,Dc = 1.587 Mg/m3,R = 0.0306,wR = 0.0619,F(000) = 936.The Br…p interactions,hydrogen bonds,aromatic hy-drogen bonds and aromatic stacking interactions exist in the crystal structures of 1 and 2,which lead them into supramolecular compounds with a three-dimensional network structure,respec-tively.1 and 2 are the isoflavanone derivatives halogenated at C3 and this kind of isoflavanone halides has not been reported yet.展开更多
文摘The trifluoromethylthio group （SCF3） is a fluorine chemotype that has experienced a strong acceleration of in- terest in the recent years. It is particularly true of the construction of new fluorinated architectures by electrophilic trifluoromethylthiolation. The spread of knowledge was already very active in this research domain in the sixties; however, gaseous and highly toxic trifluoromethanesulfenyl chloride （CF3SC1） was the only reagent available at that time. Nowadays, one really can speak of a revival in the field thanks to the rapid development of a wide pano- ply of reagents that are stable and easy to handle. This review provides a historical perspective of the development of shelf-stable electrophilic trifluoromethylthiolation reagents.
基金the National Natural Science Foundation of China(Nos.22071149,21871178)the Natural Science Foundation of Shanghai(23ZR1428200)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning for financial support.
文摘Lewis base catalyzed and Brønsted acid controlled chemodivergent electrophilic selenofunctionalizations of alkynes were developed for the first time.Various selenium-containing tetrasubstituted alkenes were readily obtained in moderate to excellent yields with complete E/Z selectivities.As the substrates were 1-ethynyl naphthol derivatives,linear selenium-containing tetrasubstituted alkenes were produced via intermolecular oxygen nucleophilic attack in the absence of acid additive;in contrast,cyclic selenium-containing tetrasubstituted alkenes were generated through intramolecular carbon nucleophilic capture with the addition of Brønsted acid.
文摘Two novel compounds,3,8-dibromo-2-methoxyl-7-isopropoxyisoflavanone (1) and 3,6-dibromo-2-methoxyl-7-isopropoxyisoflavanone (2),are synthesized via bromination reaction of their precursor ipriflavone in methanol.The mixture of 1 and 2 co-crystallizes in ethanol and forms two different crystal shapes,the shape of 1 being block and 2 prism,they can be separated manually.1 and 2 are characterized by IR,1H NMR and single crystal X-ray diffraction.The mechanism of bromination reaction is also discussed.1 crystallizes in the monoclinic space group P 21/n with cell parameters a = 1.3569(3) nm,b = 0.6706(2) nm,c = 2.0704(4) nm,?= 97.50(2)°,V = 1.8678(6) nm3,Z = 4,Dc = 1.672 Mg/m3,R = 0.0455,wR = 0.0779,F(000) = 936.2 crystallizes in the monoclinic space group P 21/c with cell parameters a =1.3854(17) nm,b = 1.1215(14) nm,c = 1.3038(17) nm,? = 103.71(2)°,V = 1.968(4) nm3,Z = 4,Dc = 1.587 Mg/m3,R = 0.0306,wR = 0.0619,F(000) = 936.The Br…p interactions,hydrogen bonds,aromatic hy-drogen bonds and aromatic stacking interactions exist in the crystal structures of 1 and 2,which lead them into supramolecular compounds with a three-dimensional network structure,respec-tively.1 and 2 are the isoflavanone derivatives halogenated at C3 and this kind of isoflavanone halides has not been reported yet.
