Herein,we report a distinctive and marvelous dual-migration of alkynyl tetracoordinate borons activated by both hydrochloric acid(HCl)and N-chlorosuccinimide(NCS),which is significantly different from conventional mig...Herein,we report a distinctive and marvelous dual-migration of alkynyl tetracoordinate borons activated by both hydrochloric acid(HCl)and N-chlorosuccinimide(NCS),which is significantly different from conventional migration modes under basic conditions.In this protocol,HCl,as the first electrophile,activates the C≡C bond,triggering the first 1,2-aryl migration.Subsequently,NCS promotes a secondary metallate shift,enabling the construction of polysubstituted alkenes.Notably,this process can work well under mild conditions,exhibits high efficiency,and provides valuable products.This transformation reveals that Zweifel olefination is not just limited to traditional basic conditions,it can proceed smoothly under acidic conditions as well,which greatly expands the scope of this well-known olefination reaction.展开更多
Mononuclear copper（Ⅱ）, nickel（Ⅱ） and cobalt（Ⅲ） tetracoordinate macrocyclic complexes were synthesized and spectroscopically characterized. The crystal structure of the three compounds were determined by X-ray...Mononuclear copper（Ⅱ）, nickel（Ⅱ） and cobalt（Ⅲ） tetracoordinate macrocyclic complexes were synthesized and spectroscopically characterized. The crystal structure of the three compounds were determined by X-ray crystallography. The electrochemical experimental results indicate that the three complexes could interact with DNA mainly by electrostatic interaction. The interaction of tetracoordinate macrocyclic cobalt（Ⅲ） complex with DNA was studied by cyclic voltammetry and UV-vis spectroscopy. The experimental results reveal that tetracoordinate macrocyc- lic cobalt（Ⅲ） complex could interact with DNA by electrostatic interaction to form a 1 ： 1 DNA association complex with a binding constant of 7.50 ×10^3 L·mol^-1.展开更多
Compared with well-developed radical aromatic ring migration,heteroatomic radical migration and alkenyl radical migration remain challenging.Herein,a photoinduced remote radical migration reaction based on the aromati...Compared with well-developed radical aromatic ring migration,heteroatomic radical migration and alkenyl radical migration remain challenging.Herein,a photoinduced remote radical migration reaction based on the aromatic skeleton through tetracoordinate boron species has been developed.In this work,commercially available diboron reagent(B2pin2)or alkenyl boron(alkenylBpin)react with o-bromostyrenes as well as their analogues under the mediation of lithium reagents in a single-vessel reaction.This process undergoes an interesting 1,4-,1,5-or 1,6-remote radical migration via intramolecular circular transition state,which introduces a large array of boron-migrative or alkenyl-migrative compounds.In particular,the 1,6-radical migration reaction has not been reported before.This protocol features readily accessible starting materials,high atom economy,broad substrate scope and diversified valuable products with Csp3-B and Csp2-B bonds obtained simultaneously with B2pin2 or portrays alkenyl-migrative module and excellent E/Z selectivity with alkenylBpins.展开更多
基金the financial support from the National Key Research&Development Program of China(2023YFF0723900)the National Natural Science Foundation of China(22271105)+3 种基金the Natural Science Foundation of Fujian Province(2022J02009)the Open Research Fund of State Key Laboratory of Coordination ChemistrySchool of Chemistry and Chemical Engineering,Nanjing Universitythe Hubei Key Laboratory of Pollutant Analysis&Reuse Technology Open Foundation(PA240102)。
文摘Herein,we report a distinctive and marvelous dual-migration of alkynyl tetracoordinate borons activated by both hydrochloric acid(HCl)and N-chlorosuccinimide(NCS),which is significantly different from conventional migration modes under basic conditions.In this protocol,HCl,as the first electrophile,activates the C≡C bond,triggering the first 1,2-aryl migration.Subsequently,NCS promotes a secondary metallate shift,enabling the construction of polysubstituted alkenes.Notably,this process can work well under mild conditions,exhibits high efficiency,and provides valuable products.This transformation reveals that Zweifel olefination is not just limited to traditional basic conditions,it can proceed smoothly under acidic conditions as well,which greatly expands the scope of this well-known olefination reaction.
基金Project supported by the Program for New Century Excellent Talents in University （No. NCET-04-0649） and Science Foundation of China （Nos 20275020 and 20475030）.
文摘Mononuclear copper（Ⅱ）, nickel（Ⅱ） and cobalt（Ⅲ） tetracoordinate macrocyclic complexes were synthesized and spectroscopically characterized. The crystal structure of the three compounds were determined by X-ray crystallography. The electrochemical experimental results indicate that the three complexes could interact with DNA mainly by electrostatic interaction. The interaction of tetracoordinate macrocyclic cobalt（Ⅲ） complex with DNA was studied by cyclic voltammetry and UV-vis spectroscopy. The experimental results reveal that tetracoordinate macrocyc- lic cobalt（Ⅲ） complex could interact with DNA by electrostatic interaction to form a 1 ： 1 DNA association complex with a binding constant of 7.50 ×10^3 L·mol^-1.
基金support from the China National Key Research&Development Program(grant no.2023YFF0723900)National Natural Science Foundation of China(grant nos.21931013 and 22271105)+1 种基金the Natural Science Foundation of Fujian Province(grant no.2022J02009)Fuzhou University(grant no.510578)are gratefully acknowledged。
文摘Compared with well-developed radical aromatic ring migration,heteroatomic radical migration and alkenyl radical migration remain challenging.Herein,a photoinduced remote radical migration reaction based on the aromatic skeleton through tetracoordinate boron species has been developed.In this work,commercially available diboron reagent(B2pin2)or alkenyl boron(alkenylBpin)react with o-bromostyrenes as well as their analogues under the mediation of lithium reagents in a single-vessel reaction.This process undergoes an interesting 1,4-,1,5-or 1,6-remote radical migration via intramolecular circular transition state,which introduces a large array of boron-migrative or alkenyl-migrative compounds.In particular,the 1,6-radical migration reaction has not been reported before.This protocol features readily accessible starting materials,high atom economy,broad substrate scope and diversified valuable products with Csp3-B and Csp2-B bonds obtained simultaneously with B2pin2 or portrays alkenyl-migrative module and excellent E/Z selectivity with alkenylBpins.
