An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I)complex as a chiral catalyst was presented.A variety of optically activeβ-naphthalenone compoun...An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I)complex as a chiral catalyst was presented.A variety of optically activeβ-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions.Mechanistic studies indicated that this Csp^(2)–N dearomatizing coupling proceeds via 1,3-reductive elimination of phenolate-Cu~Ⅲ-amino intermediate in five-membered ring transition states.The origin of enantioselectivity has also been elucidated based on density functional theory calculations.展开更多
Ligand-accelerated catalysis(LAC),a term originally coined by Sharpless,has been a pivotal guiding principle in the advancement of asymmetric catalysis.The discovery and understanding of LAC have not only energized th...Ligand-accelerated catalysis(LAC),a term originally coined by Sharpless,has been a pivotal guiding principle in the advancement of asymmetric catalysis.The discovery and understanding of LAC have not only energized the enhancement of established catalytic asymmetric transformations but also ignited the creation of novel ones.In this review,we have curated a selection of illustrative examples,delving into the profound influence that chiral ligands exert on the acceleration of Lewis acid-promoted reactions,encompassing both thermally induced and photochemical processes.The impact of a chiral ligand on various facets,including solubility,aggregation state,geometry,Lewis acidity,and photophysical properties of metal salts,has been identified as crucial determinants.Moreover,the covalent and noncovalent interactions between ligands and substrates,the creation of chiral pockets by chiral ligands and metals,as well as the alterations in the physical and chemical properties of substrates induced by Lewis acid coordination,also play significant roles.Notably,the utilization of ligandaccelerated asymmetric Lewis acid catalysis in photoreactions presents an efficient approach for addressing the challenges associated with stereocontrol.We anticipate that this review will inspire researchers to pay more attention to the role of ligands and aid in the development of new efficient ligands and asymmetric reactions.展开更多
基金supported by the National Natural Science Foundation of China(22188101)Sichuan Science and Technology Program(2021YJ0561)。
文摘An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I)complex as a chiral catalyst was presented.A variety of optically activeβ-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions.Mechanistic studies indicated that this Csp^(2)–N dearomatizing coupling proceeds via 1,3-reductive elimination of phenolate-Cu~Ⅲ-amino intermediate in five-membered ring transition states.The origin of enantioselectivity has also been elucidated based on density functional theory calculations.
基金the National Natural Science Foundation of China(grant nos.22188101 and 21890723)Sichuan University(grant no.2020SCUNL204)for financial support。
文摘Ligand-accelerated catalysis(LAC),a term originally coined by Sharpless,has been a pivotal guiding principle in the advancement of asymmetric catalysis.The discovery and understanding of LAC have not only energized the enhancement of established catalytic asymmetric transformations but also ignited the creation of novel ones.In this review,we have curated a selection of illustrative examples,delving into the profound influence that chiral ligands exert on the acceleration of Lewis acid-promoted reactions,encompassing both thermally induced and photochemical processes.The impact of a chiral ligand on various facets,including solubility,aggregation state,geometry,Lewis acidity,and photophysical properties of metal salts,has been identified as crucial determinants.Moreover,the covalent and noncovalent interactions between ligands and substrates,the creation of chiral pockets by chiral ligands and metals,as well as the alterations in the physical and chemical properties of substrates induced by Lewis acid coordination,also play significant roles.Notably,the utilization of ligandaccelerated asymmetric Lewis acid catalysis in photoreactions presents an efficient approach for addressing the challenges associated with stereocontrol.We anticipate that this review will inspire researchers to pay more attention to the role of ligands and aid in the development of new efficient ligands and asymmetric reactions.
