A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition m...A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K<sub>3</sub>PO<sub>4</sub>) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .展开更多
Henry reaction is one of the most classical reactions to construct synthetically useful product nitro alcohol, which as a privileged skeleton is widely distributed in various pharmaceuticals. This review summarizes th...Henry reaction is one of the most classical reactions to construct synthetically useful product nitro alcohol, which as a privileged skeleton is widely distributed in various pharmaceuticals. This review summarizes the recent progress of copper-catalyzed asymmetric Henry reaction from 2011 to 2016. The significant progress that has been made in this area will be highlighted and some of challenges that the author believes may be hindering further progress will be revealed.展开更多
An efficient and scalable electrochemical asymmetric protocol with metal-free catalysts and even without additional oxidants for the cross-dehydrogenative coupling reaction(CDC)of two C(sp^(3))-H bonds is reported.A s...An efficient and scalable electrochemical asymmetric protocol with metal-free catalysts and even without additional oxidants for the cross-dehydrogenative coupling reaction(CDC)of two C(sp^(3))-H bonds is reported.A series of aldehydes including natural products and various substrates containing C(sp^(3))-H bonds including xanthenes,acridines,cycloheptatrienes and even diarylmethane have been shown to undergo asymmetric CDC to afford a series of carbon-carbon bond coupling products with up to 94%yield and 98%ee.Mechanistic studies such as radical clock experiment suggest that the reaction proceeds via nucleophilic attack by enamine under electrochemical conditions.展开更多
Due to high ring strain energies,cyclopropanols and cyclobutanols have a strong tendency of breaking theendocyclic C–C bonds to participate in versatile organic transformations.With an inherent three-dimensionalstruc...Due to high ring strain energies,cyclopropanols and cyclobutanols have a strong tendency of breaking theendocyclic C–C bonds to participate in versatile organic transformations.With an inherent three-dimensionalstructure,cyclopropanols and cyclobutanols have the advantage of synthesizing linear or cyclic molecules withstereogenic centers via ring-opening asymmetric synthesis.There are three strategies for the ring-opening ofcyclopropanols and cyclobutanols usually involved in asymmetric synthesis:1)β-carbon elimination of metalalkoxide;2)radical ring-opening;3)ring-opening via semipinacol rearrangement.The present review has high-lighted the progress developed in the last five years.展开更多
The effects of the chiral substituents attached to silicon on the stereoselectivity of the reactions of C-centered chiral silicon compounds wm examined. The investigation was focused on the asymmetric C—C bond format...The effects of the chiral substituents attached to silicon on the stereoselectivity of the reactions of C-centered chiral silicon compounds wm examined. The investigation was focused on the asymmetric C—C bond formation reaction of chiral allylsilanes and α-silylallyl anions with aldehydes. The functionalities of the substituents on silicon can be manipulated to improve the stereoselectivities of the reactions remote from silicon atom.展开更多
A direct C–H amination reaction of N-Ts-2-Styrylaniline derivatives to realize the synthesis of indole derivatives was developed in the presence of copper salt. A variety of N-Ts-2-Styrylaniline derivatives were tran...A direct C–H amination reaction of N-Ts-2-Styrylaniline derivatives to realize the synthesis of indole derivatives was developed in the presence of copper salt. A variety of N-Ts-2-Styrylaniline derivatives were transformed into the corresponding indole products in good to excellent yield under mild conditions with the oxidation of potassium persulfate.展开更多
An iron-catalyzed oxidative C-C bond formation by the reactions of simple toluene derivatives with 1,3-dicarbonyl compounds is developed.A benzylic radical addition to a benzoylmethanato iron species is proposed for t...An iron-catalyzed oxidative C-C bond formation by the reactions of simple toluene derivatives with 1,3-dicarbonyl compounds is developed.A benzylic radical addition to a benzoylmethanato iron species is proposed for the transformation.展开更多
The regio-and enantioselective functionalization of 1,3-dienes has become a powerful tool for the synthesis of allylic compounds,yet it remains a challenge for aliphatic dienes.Herein,we report a nickel-catalyzed asym...The regio-and enantioselective functionalization of 1,3-dienes has become a powerful tool for the synthesis of allylic compounds,yet it remains a challenge for aliphatic dienes.Herein,we report a nickel-catalyzed asymmetric hydroarylation reaction of aliphatic and aromatic dienes with indoles to afford chiral indole derivatives.展开更多
文摘A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K<sub>3</sub>PO<sub>4</sub>) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .
基金the National Natural Science Foundation of China (Nos. 2127222, 21432009, 21472177, J1310010)Chinese Academy of Sciences(No. XDB20000000)
文摘Henry reaction is one of the most classical reactions to construct synthetically useful product nitro alcohol, which as a privileged skeleton is widely distributed in various pharmaceuticals. This review summarizes the recent progress of copper-catalyzed asymmetric Henry reaction from 2011 to 2016. The significant progress that has been made in this area will be highlighted and some of challenges that the author believes may be hindering further progress will be revealed.
基金National Natural Science Foundation of China(Nos.22161008,22061003)Guangxi Science and Technology Base and Talent Project(High Level Innovative Talents and Team Training)(Guike No.AD23026094)Guangxi Natural Science Foundation of China(No.2021GXNSFFA220005)for financial support。
文摘An efficient and scalable electrochemical asymmetric protocol with metal-free catalysts and even without additional oxidants for the cross-dehydrogenative coupling reaction(CDC)of two C(sp^(3))-H bonds is reported.A series of aldehydes including natural products and various substrates containing C(sp^(3))-H bonds including xanthenes,acridines,cycloheptatrienes and even diarylmethane have been shown to undergo asymmetric CDC to afford a series of carbon-carbon bond coupling products with up to 94%yield and 98%ee.Mechanistic studies such as radical clock experiment suggest that the reaction proceeds via nucleophilic attack by enamine under electrochemical conditions.
基金Financial support from the Fuzhou University(No.0041/511095)is gratefully acknowledged.We also thank Liuhui Xu for drawing many chemical structures.
文摘Due to high ring strain energies,cyclopropanols and cyclobutanols have a strong tendency of breaking theendocyclic C–C bonds to participate in versatile organic transformations.With an inherent three-dimensionalstructure,cyclopropanols and cyclobutanols have the advantage of synthesizing linear or cyclic molecules withstereogenic centers via ring-opening asymmetric synthesis.There are three strategies for the ring-opening ofcyclopropanols and cyclobutanols usually involved in asymmetric synthesis:1)β-carbon elimination of metalalkoxide;2)radical ring-opening;3)ring-opening via semipinacol rearrangement.The present review has high-lighted the progress developed in the last five years.
文摘The effects of the chiral substituents attached to silicon on the stereoselectivity of the reactions of C-centered chiral silicon compounds wm examined. The investigation was focused on the asymmetric C—C bond formation reaction of chiral allylsilanes and α-silylallyl anions with aldehydes. The functionalities of the substituents on silicon can be manipulated to improve the stereoselectivities of the reactions remote from silicon atom.
基金financially supported by the National Natural Science Foundation of China(Nos.21272169,21302135)the Key Innovation Team of Science & Technology in Zhejiang Province(No.2010R50018-10)+1 种基金the Science and Technology Bureau of Taizhou(No.08KY10)the Key Disciplines of Applied Chemistry of Zhejiang Province,Taizhou University
文摘A direct C–H amination reaction of N-Ts-2-Styrylaniline derivatives to realize the synthesis of indole derivatives was developed in the presence of copper salt. A variety of N-Ts-2-Styrylaniline derivatives were transformed into the corresponding indole products in good to excellent yield under mild conditions with the oxidation of potassium persulfate.
基金supported by the National Natural Science Foundation of China (20832002 and 21072223)the Fundamental Research Funds for the Central Universitiesthe Research Funds of Renmin University of China (10XNL017)
文摘An iron-catalyzed oxidative C-C bond formation by the reactions of simple toluene derivatives with 1,3-dicarbonyl compounds is developed.A benzylic radical addition to a benzoylmethanato iron species is proposed for the transformation.
基金the National Natural Science Foundation of China(nos.21790330 and 91956000)and the“111”Project(no.B06005)of the Ministry of Education of China for financial support.
文摘The regio-and enantioselective functionalization of 1,3-dienes has become a powerful tool for the synthesis of allylic compounds,yet it remains a challenge for aliphatic dienes.Herein,we report a nickel-catalyzed asymmetric hydroarylation reaction of aliphatic and aromatic dienes with indoles to afford chiral indole derivatives.
