1,1-Diaryl moieties are core structures in a wide range of bioactive and pharmaceutical compounds.Transition-metal catalysis is a convenient approach to accessing these invaluable compounds affording high yields and e...1,1-Diaryl moieties are core structures in a wide range of bioactive and pharmaceutical compounds.Transition-metal catalysis is a convenient approach to accessing these invaluable compounds affording high yields and enantioselectivities.This review summarizes 1,1-diarylalkanes synthesis through transition metal catalysis.Particular focus is given to recent developments,such as reductive cross-electrophile couplings,benzylic C–H bond arylation,transformations involving metal migration,asymmetric hydrogenation of 1,1-diarylalkenes and three-component coupling reactions.展开更多
Synthesis of organosilanes from alkenes is a very important topic owing to their wide applications.A Ni/Cu dual metal-catalyzed arylsilylation of terminal alkenes,featuring migratory selectivity,has been developed.A w...Synthesis of organosilanes from alkenes is a very important topic owing to their wide applications.A Ni/Cu dual metal-catalyzed arylsilylation of terminal alkenes,featuring migratory selectivity,has been developed.A wide diversity of aliphatic silanes have been prepared from terminal alkenes,aryl halides and Suginome’s reagent.This protocol is highlighted by excellent regioselectivity,mild reaction conditions and good functional group tolerance.In addition to benzylic positions,carbon–carbon bonds can also be constructed at allylic positions.Preliminary mechanistic studies suggest that the copper cocatalyst promotes the transmetalation of Suginome’s reagent,and the addition of a Pyr Ox ligand inhibits the formation of side-products from the carbon-Heck pathway.Moreover,studies toward the nature of the Pyr Ox ligand revealed that the steric hindrance of the oxazoline moiety greatly affects the chain–walking process,but not the arylation step.展开更多
Regiodivergent catalysis provides an efficient strategic approach for the construction of architecturally different molecules from the same starting materials. In this field, the intermolecular regiodivergent 1,2-difu...Regiodivergent catalysis provides an efficient strategic approach for the construction of architecturally different molecules from the same starting materials. In this field, the intermolecular regiodivergent 1,2-difunctionalization of alkenes with two electrophiles is still a challenging task. A ligand-controlled, nickel-catalyzed regiodivergent dicarbofunctionalization of alkenes using both aryl/vinyl halides and acetals as electrophiles under mild reductive reaction conditions has been accomplished. This study provides a general approach to accessing both β-methoxyl esters and γ-methoxyl esters from readily available acrylates,aryl halides and acetals. Experimental mechanistic evidence supports that the difference in regioselective outcomes is attributed to the ligand tuning the reactivity of the nickel catalyst, which results in different catalytic cycles operating for these two reaction conditions.展开更多
基金supported by the National Natural Science Foundation of China(21702151,21871211)the Fundamental Research Funds for Central Universities(2042019kf0208)。
文摘1,1-Diaryl moieties are core structures in a wide range of bioactive and pharmaceutical compounds.Transition-metal catalysis is a convenient approach to accessing these invaluable compounds affording high yields and enantioselectivities.This review summarizes 1,1-diarylalkanes synthesis through transition metal catalysis.Particular focus is given to recent developments,such as reductive cross-electrophile couplings,benzylic C–H bond arylation,transformations involving metal migration,asymmetric hydrogenation of 1,1-diarylalkenes and three-component coupling reactions.
基金supported by the National Natural Science Foundation of China(21702151,21774029,and 21871211)the Fundamental Research Funds for Central Universities(2042019kf0208)。
文摘Synthesis of organosilanes from alkenes is a very important topic owing to their wide applications.A Ni/Cu dual metal-catalyzed arylsilylation of terminal alkenes,featuring migratory selectivity,has been developed.A wide diversity of aliphatic silanes have been prepared from terminal alkenes,aryl halides and Suginome’s reagent.This protocol is highlighted by excellent regioselectivity,mild reaction conditions and good functional group tolerance.In addition to benzylic positions,carbon–carbon bonds can also be constructed at allylic positions.Preliminary mechanistic studies suggest that the copper cocatalyst promotes the transmetalation of Suginome’s reagent,and the addition of a Pyr Ox ligand inhibits the formation of side-products from the carbon-Heck pathway.Moreover,studies toward the nature of the Pyr Ox ligand revealed that the steric hindrance of the oxazoline moiety greatly affects the chain–walking process,but not the arylation step.
基金supported by the National Natural Science Foundation of China (21871211, 21774029, 22122107)the Fundamental Research Funds for Central Universities (2042019kf0208)。
文摘Regiodivergent catalysis provides an efficient strategic approach for the construction of architecturally different molecules from the same starting materials. In this field, the intermolecular regiodivergent 1,2-difunctionalization of alkenes with two electrophiles is still a challenging task. A ligand-controlled, nickel-catalyzed regiodivergent dicarbofunctionalization of alkenes using both aryl/vinyl halides and acetals as electrophiles under mild reductive reaction conditions has been accomplished. This study provides a general approach to accessing both β-methoxyl esters and γ-methoxyl esters from readily available acrylates,aryl halides and acetals. Experimental mechanistic evidence supports that the difference in regioselective outcomes is attributed to the ligand tuning the reactivity of the nickel catalyst, which results in different catalytic cycles operating for these two reaction conditions.
