3d-Metal-catalyzed tertiary C(sp^(3))–H bond activation has been a formidable challenge.Herein,a tertiary C(sp^(3))–H bond is smoothly activated by Ni–Al bimetallic catalysts for dual C–H annulation of formamides ...3d-Metal-catalyzed tertiary C(sp^(3))–H bond activation has been a formidable challenge.Herein,a tertiary C(sp^(3))–H bond is smoothly activated by Ni–Al bimetallic catalysts for dual C–H annulation of formamides with alkynes,delivering a series of δ-lactams with a quaternary carbon up to 98%yield.Various tertiary C(sp^(3))–H bonds such as noncyclic,monocyclic and bridged-ring tertiary C(sp^(3))–H bonds are all compatible with the reaction.展开更多
1.Introduction The past few decades have witnessed extensive studies on transition metal-catalyzed C-H bond activations and subsequent carbon-carbon and/or carbon-heteroatom bond formations because these methods provi...1.Introduction The past few decades have witnessed extensive studies on transition metal-catalyzed C-H bond activations and subsequent carbon-carbon and/or carbon-heteroatom bond formations because these methods provide more atom-and step-economical pathways than those traditional transformations starting from prefunctionalized substrates.展开更多
Following the age of directing group,anchoring catalysis starts coming to the center of the stage.Different from the directinggroup strategy that needs a preinstalled directing group in substrates,anchoring catalysis ...Following the age of directing group,anchoring catalysis starts coming to the center of the stage.Different from the directinggroup strategy that needs a preinstalled directing group in substrates,anchoring catalysis relies on a reversible interaction between a substrate and a catalyst,which then directs metal to activate inert chemical bonds.Such reversible directing effect not only generates good site-and stereo-selectivity as traditional directing groups do but also eliminates the requirement of stoichiometric amounts of directing groups.Among variously reported anchoring catalysis,coordinative bimetallic anchoring catalysis in general displays superior reactivity than others because coordinative bonding not only affords strong interaction of catalysts with substrates but also displays good compatibility with substrates and reaction conditions.In recent years,big progress has been achieved for coordinative bimetallic anchoring catalysis.This review gave a detailed summary of this field,including catalyst development,catalyst types,reaction types and reaction mechanisms.展开更多
A nickel-catalyzed reductive coupling of aldehydes with aikynes using 1-phenylethanol as reducing agent has been developed.The key achievement of this work is that we demonstrate environmentally benign 1-phenylethanol...A nickel-catalyzed reductive coupling of aldehydes with aikynes using 1-phenylethanol as reducing agent has been developed.The key achievement of this work is that we demonstrate environmentally benign 1-phenylethanol can serve as a viable alternative reducing agent to Et3B,ZnEt2 and R3SiH for the nickel-catalyzed reductive coupling reaction of aldehyde and alkynes.展开更多
Ni-Al bimetallic catalysis proves to be an efficient catalytic strategy for unreactive bond transformations. Recently, chiral bifunctional ligands, especially amphoteric secondary phosphine oxide(SPO) ligand, are used...Ni-Al bimetallic catalysis proves to be an efficient catalytic strategy for unreactive bond transformations. Recently, chiral bifunctional ligands, especially amphoteric secondary phosphine oxide(SPO) ligand, are used for a more powerful synergistic effect in the bimetal-catalyzed reactions, providing not only milder reaction conditions and higher reactivity but also excellent reaction selectivity. Herein, we give a brief review on the development of Ni-Al bimetallic catalytic system and highlight recent advances in enantioselective Ni-Al bimetallic catalysis for unreactive bond transformation.展开更多
Due to the lack of proper chralgands,enantioselectve C(sp^2)-H borylation has been a challenging goalfor a long time.Recently,threedifferent types ofwel-designed chiral ligands were developed,not only addressing this ...Due to the lack of proper chralgands,enantioselectve C(sp^2)-H borylation has been a challenging goalfor a long time.Recently,threedifferent types ofwel-designed chiral ligands were developed,not only addressing this challenge but also providing a good inspiration for the future development of otherasymmetric reactions.展开更多
Dienols are important structural motifs in organic molecules,but most of the traditional synthetic methods required multistep prefunctionalization of substrates,leading to stoichiometric waste and low atom economy.Her...Dienols are important structural motifs in organic molecules,but most of the traditional synthetic methods required multistep prefunctionalization of substrates,leading to stoichiometric waste and low atom economy.Herein,we report a redox-neutral coupling of simple 1,3-dienes and aldehydes via nickel and Brønsted acid dual catalysis,providing a highly atom-economical and by-product-free route to various dienols with up to 94%yield and up to 50∶1 EE/EZ ratio.The use of 2-isopropoxyphenol as a Brønsted acid co-catalyst was critical to the reactivity and selectivity.展开更多
基金the National Key R&D Program of China(grant no.2022YFA1504300)the National Natural Science Foundation of China(grant nos.22188101 and 22325103)+1 种基金the Haihe Laboratory of Sustainable Chemical Transformations and“Frontiers Science Center for New Organic Matter,”Nankai University(grant no.63181206)the Fundamental Research Funds for the Central Universities for financial support.
文摘3d-Metal-catalyzed tertiary C(sp^(3))–H bond activation has been a formidable challenge.Herein,a tertiary C(sp^(3))–H bond is smoothly activated by Ni–Al bimetallic catalysts for dual C–H annulation of formamides with alkynes,delivering a series of δ-lactams with a quaternary carbon up to 98%yield.Various tertiary C(sp^(3))–H bonds such as noncyclic,monocyclic and bridged-ring tertiary C(sp^(3))–H bonds are all compatible with the reaction.
基金We thank the National Natural Science Foundation of China (Nos. 21871145, 21672107 and 91856104) for financial support.
文摘1.Introduction The past few decades have witnessed extensive studies on transition metal-catalyzed C-H bond activations and subsequent carbon-carbon and/or carbon-heteroatom bond formations because these methods provide more atom-and step-economical pathways than those traditional transformations starting from prefunctionalized substrates.
基金supported by the National Natural Science Foundation of China(91856104,21871145)the Tianjin Applied Basic Research Project and Cutting-Edge Technology Research Plan(19JCZDJC37900)“Frontiers Science Center for New Organic Matter”,Nankai University(63181206)。
文摘Following the age of directing group,anchoring catalysis starts coming to the center of the stage.Different from the directinggroup strategy that needs a preinstalled directing group in substrates,anchoring catalysis relies on a reversible interaction between a substrate and a catalyst,which then directs metal to activate inert chemical bonds.Such reversible directing effect not only generates good site-and stereo-selectivity as traditional directing groups do but also eliminates the requirement of stoichiometric amounts of directing groups.Among variously reported anchoring catalysis,coordinative bimetallic anchoring catalysis in general displays superior reactivity than others because coordinative bonding not only affords strong interaction of catalysts with substrates but also displays good compatibility with substrates and reaction conditions.In recent years,big progress has been achieved for coordinative bimetallic anchoring catalysis.This review gave a detailed summary of this field,including catalyst development,catalyst types,reaction types and reaction mechanisms.
基金We thank the National Natural Science Foundation of China(Nos.21672107,91856104 and 21871145)"the Fundamental Research Funds for the Central Universities",Nankai University(No.63191601)for financial support.
文摘A nickel-catalyzed reductive coupling of aldehydes with aikynes using 1-phenylethanol as reducing agent has been developed.The key achievement of this work is that we demonstrate environmentally benign 1-phenylethanol can serve as a viable alternative reducing agent to Et3B,ZnEt2 and R3SiH for the nickel-catalyzed reductive coupling reaction of aldehyde and alkynes.
基金supported by the National Natural Science Foundation of China (21672107)the “1000-Youth Talents Plan”
文摘Ni-Al bimetallic catalysis proves to be an efficient catalytic strategy for unreactive bond transformations. Recently, chiral bifunctional ligands, especially amphoteric secondary phosphine oxide(SPO) ligand, are used for a more powerful synergistic effect in the bimetal-catalyzed reactions, providing not only milder reaction conditions and higher reactivity but also excellent reaction selectivity. Herein, we give a brief review on the development of Ni-Al bimetallic catalytic system and highlight recent advances in enantioselective Ni-Al bimetallic catalysis for unreactive bond transformation.
基金We thank the National Natural Science Foundation of China(91856104,,21871145 and 21672107)the Tianjin Applied BasicResearch Project and cutting-Edge Technology Research Plan(19JCZDJC37900)the Fundamental Research Funds for theCentral Universities"(63191601)for financial support.
文摘Due to the lack of proper chralgands,enantioselectve C(sp^2)-H borylation has been a challenging goalfor a long time.Recently,threedifferent types ofwel-designed chiral ligands were developed,not only addressing this challenge but also providing a good inspiration for the future development of otherasymmetric reactions.
基金the National Natural Science Foundation of China(21672107 and 21871145)the Fundamental Research Funds for the Central Universities(Nankai University,63191601)the Tianjin Applied Basic Research Project and Cutting-Edge Technology Research Plan(19JCZDJC37900)for financial support.
文摘Dienols are important structural motifs in organic molecules,but most of the traditional synthetic methods required multistep prefunctionalization of substrates,leading to stoichiometric waste and low atom economy.Herein,we report a redox-neutral coupling of simple 1,3-dienes and aldehydes via nickel and Brønsted acid dual catalysis,providing a highly atom-economical and by-product-free route to various dienols with up to 94%yield and up to 50∶1 EE/EZ ratio.The use of 2-isopropoxyphenol as a Brønsted acid co-catalyst was critical to the reactivity and selectivity.
