Comprehensive Summary:The reaction site of aryl diazonium salt was restricted in the position of diazonium moiety,due to the intrinsic electrophilicity of diazonium moiety.Herein,we described an unprecedented chemosel...Comprehensive Summary:The reaction site of aryl diazonium salt was restricted in the position of diazonium moiety,due to the intrinsic electrophilicity of diazonium moiety.Herein,we described an unprecedented chemoselective alkylation of Csp2-H of aryl diazonium salts with 1-iodo-3-pentafluorosulfanylbicyclo[1,1,1]pentane(SF5-BCP-I).This novel alkylation of aryl diazonium salts provided an efficient access to various SF5-BCP substituted aromatics that might have great potential application in the drug discovery.Mechanistic experiments and theoretical studies revealed that the intrinsic electrophilic SF5-BCP radical resulted in the thermodynamic favorable radical addition on Csp2-H site rather than diazonium moiety of aryl diazonium salt.展开更多
Conjugate addition and allylic substitution are two essential chemical transformations,and they could be competitive for substrates with multiple reactive sites.Herein,we report the diversified enantioselective synthe...Conjugate addition and allylic substitution are two essential chemical transformations,and they could be competitive for substrates with multiple reactive sites.Herein,we report the diversified enantioselective synthesis of cyclobutenes via the functionalization of cyclobutenones.The conjugate addition of cyclobutenones with arylzinc halides provided enantioenriched cyclobutenes with all-carbon quaternary centers.On the other hand,when cyclobutenones with gem-dichloro groups were employed,a chemo-and enantioselective allylic substitution occurred.Further synthetic utility was demonstrated for synthesizing versatile cyclobutane derivatives,together with ring-opening and expansion products.展开更多
基金The National Natural Science Foundation of China(21991211,22301306,22271298)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0590000)National Key Research and Development Program of China(2021YFF0701700)are greatly acknowledged for funding this work.
文摘Comprehensive Summary:The reaction site of aryl diazonium salt was restricted in the position of diazonium moiety,due to the intrinsic electrophilicity of diazonium moiety.Herein,we described an unprecedented chemoselective alkylation of Csp2-H of aryl diazonium salts with 1-iodo-3-pentafluorosulfanylbicyclo[1,1,1]pentane(SF5-BCP-I).This novel alkylation of aryl diazonium salts provided an efficient access to various SF5-BCP substituted aromatics that might have great potential application in the drug discovery.Mechanistic experiments and theoretical studies revealed that the intrinsic electrophilic SF5-BCP radical resulted in the thermodynamic favorable radical addition on Csp2-H site rather than diazonium moiety of aryl diazonium salt.
基金supported by the National Natural Science Foundation of China(22071028,21921003).
文摘Conjugate addition and allylic substitution are two essential chemical transformations,and they could be competitive for substrates with multiple reactive sites.Herein,we report the diversified enantioselective synthesis of cyclobutenes via the functionalization of cyclobutenones.The conjugate addition of cyclobutenones with arylzinc halides provided enantioenriched cyclobutenes with all-carbon quaternary centers.On the other hand,when cyclobutenones with gem-dichloro groups were employed,a chemo-and enantioselective allylic substitution occurred.Further synthetic utility was demonstrated for synthesizing versatile cyclobutane derivatives,together with ring-opening and expansion products.
