Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules.Ynones are good regional selectivity radical acceptors in orga...Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules.Ynones are good regional selectivity radical acceptors in organic synthesis,and many of bio-relevant cyclic compounds could be easily obtained by direct radical cyclization reaction.Here,we report a photocatalytic cascade radical addition of biaryl ynones,for the divergent synthesis of privileged carbon cycles.Additionally,further transformation of the multi-functional group product into a variety of other derivatives demonstrates the synthetic value of this developed method.展开更多
Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct yn...Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date.Herein,we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashiratype approach(acyl-Pd(Ⅱ)species generated from nucleophiles).By using cyclic diaryliodonium salts as prochiral substrates,various axial chiral ynones with good functional group tolerance(39 examples),satisfied yields(71%-96%)and excellent enantioselectivities(generally 94%-99%ee)were produced.Synthesis of bioactive compounds,scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.展开更多
The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-1,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling react...The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-1,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling reaction of terminal alkynes with different acyl chlorides in the presence of triethylamine as base,giving excellent ynones under aerobic conditions.展开更多
An efficient method for asymmetric synthesis of acyclic α-tertiary amine derivatives has been achieved through enantioselective aminations of α-branched ynones with azodicarboxylates enabled by chiral phosphoric aci...An efficient method for asymmetric synthesis of acyclic α-tertiary amine derivatives has been achieved through enantioselective aminations of α-branched ynones with azodicarboxylates enabled by chiral phosphoric acid catalysis.Moreover,kinetic resolution of racemic starting material was realized under these conditions,which gave access to valuable enantioenriched α-substituted ketones.展开更多
The reactions of neutral pyrrolyl-functionalized indole with rare-earth metal amides [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 produced the rare-earth metal complexes [(Me3Si)2N]2RE([η1:μ-η2-3-(2-(N–CH3)C4H3NCH=N–CH2CH2)C8H5...The reactions of neutral pyrrolyl-functionalized indole with rare-earth metal amides [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 produced the rare-earth metal complexes [(Me3Si)2N]2RE([η1:μ-η2-3-(2-(N–CH3)C4H3NCH=N–CH2CH2)C8H5N])(μ-Cl)Li(THF)(RE = Er, Y) having indolyl ligand η1 bonded to rare-earth metal ion and η2 bonded to lithium ion. The catalytic activities of these lanthanide amido complexes for addition of terminal alkynes to aromatic nitriles were explored. Results reveal that these complexes displayed a good catalytic activity for the addition reaction under mild conditions.展开更多
The cascade reactions of alkyl α-diazoesters and ynones using Al(OTf)_(3) as the catalyst are described.A series of 4-substituted pyrazoles were obtained via [3+2] cycloaddition,1,5-ester shift,1,3-H shift,and N-H in...The cascade reactions of alkyl α-diazoesters and ynones using Al(OTf)_(3) as the catalyst are described.A series of 4-substituted pyrazoles were obtained via [3+2] cycloaddition,1,5-ester shift,1,3-H shift,and N-H insertion process.Deuterium labelling experiments,kinetic studies and control experiments were carried out for the rationalization of the mechanism.展开更多
基金the Natural Science Foundation of Zhejiang Province(LY22B020001)the Zhejiang Public Welfare Public Research Program(LGC22B010001)the National Natural Science Foundation of China(32201238)is greatly acknowledged.
文摘Functionalized free radical addition/cyclization reactions represent an efficient way for introducing new functionality or coupling fragments to molecules.Ynones are good regional selectivity radical acceptors in organic synthesis,and many of bio-relevant cyclic compounds could be easily obtained by direct radical cyclization reaction.Here,we report a photocatalytic cascade radical addition of biaryl ynones,for the divergent synthesis of privileged carbon cycles.Additionally,further transformation of the multi-functional group product into a variety of other derivatives demonstrates the synthetic value of this developed method.
基金supported financially by National Nature Science Foundation of China(No.22171258)the Youth Innovation Promotion Association CAS(No.2022375)+1 种基金the Biological Resources Programme,Chinese Academy of Sciences(No.KFJ-BRP-008)the Sichuan Science and Technology Program(No.2022ZYD0038)。
文摘Ynones are important skeletons in bioactive molecules and valuable building blocks for organic synthesis,thus great efforts have been devoted to their preparation.While,introducing prochiral substrates to construct ynones bearing a chiral framework is unrealized to date.Herein,we reported the first example of Pd/SOP-catalyzed asymmetric carbonylative alkynylation via a non-classical carbonylative Sonogashiratype approach(acyl-Pd(Ⅱ)species generated from nucleophiles).By using cyclic diaryliodonium salts as prochiral substrates,various axial chiral ynones with good functional group tolerance(39 examples),satisfied yields(71%-96%)and excellent enantioselectivities(generally 94%-99%ee)were produced.Synthesis of bioactive compounds,scale-up experiment and useful transformations were also conducted to demonstrate the utility of this process.
基金the Research Council of Shahrood University of Technology for the support of this work
文摘The palladium-salen complex palladium(Ⅱ) N,N'-bis{[5-(triphenylphosphonium)-methyl]salicylidene}-1,2-ethanediamine chloride was found to be a highly active catalyst for the copper- and solvent-free coupling reaction of terminal alkynes with different acyl chlorides in the presence of triethylamine as base,giving excellent ynones under aerobic conditions.
基金NSFC(Grant No.22171186)ShanghaiTech University start-up funding for financial supportthe support from Analytical Instrumentation Center(contract no.SPST-AIC10112914),SPST,ShanghaiTech University,and Dr.Na Yu for the X-ray crystallographic analysis.
文摘An efficient method for asymmetric synthesis of acyclic α-tertiary amine derivatives has been achieved through enantioselective aminations of α-branched ynones with azodicarboxylates enabled by chiral phosphoric acid catalysis.Moreover,kinetic resolution of racemic starting material was realized under these conditions,which gave access to valuable enantioenriched α-substituted ketones.
基金supported by the National Natural Science Foundation of China (21202002, 21372010)the National Basic Research Program of China (2012CB821600)grants from the Ministry of Education (20103424110001) and Anhui Province (KJ2012A138)
文摘The reactions of neutral pyrrolyl-functionalized indole with rare-earth metal amides [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 produced the rare-earth metal complexes [(Me3Si)2N]2RE([η1:μ-η2-3-(2-(N–CH3)C4H3NCH=N–CH2CH2)C8H5N])(μ-Cl)Li(THF)(RE = Er, Y) having indolyl ligand η1 bonded to rare-earth metal ion and η2 bonded to lithium ion. The catalytic activities of these lanthanide amido complexes for addition of terminal alkynes to aromatic nitriles were explored. Results reveal that these complexes displayed a good catalytic activity for the addition reaction under mild conditions.
基金supported by the National Natural Science Foundation of China(Nos.21625205 and U19A2014)。
文摘The cascade reactions of alkyl α-diazoesters and ynones using Al(OTf)_(3) as the catalyst are described.A series of 4-substituted pyrazoles were obtained via [3+2] cycloaddition,1,5-ester shift,1,3-H shift,and N-H insertion process.Deuterium labelling experiments,kinetic studies and control experiments were carried out for the rationalization of the mechanism.
