Danxing Wu

Abstract The ubiquitous nature of amines in drug compounds, bioactive molecules and natural products has fueled intense interest in their synthesis. Herein, we introduce a nickel‐catalyzed enantioconvergent allenylic amination of methanol‐activated allenols. This protocol affords a diverse array of functionalized allenylic amines in high yields and with excellent enantioselectivities. The synthetic potential of this method is demonstrated by employing bioactive amines as nucleophiles and conducting gram‐scale reactions. Furthermore, mechanistic investigations and DFT calculations elucidate the role of methanol as an activator in the nickel‐catalyzed reaction, facilitating the oxidative addition of the C−O bond of allenols through hydrogen‐bonding interactions. The remarkable outcomes arise from a rapid racemization of allenols enabled by the nickel catalyst and from highly enantioselective dynamic kinetic asymmetric transformation of η 3 ‐alkadienylnickel intermediates.

In recent years, manganese dioxide cathodes have demonstrated unparalleled benefits in aqueous zinc-ion batteries (AZIBs) and aqueous zinc-ion hybrid capacitors (AZICs) owing to their high discharge voltage (∼1.4 V), abundant resources, nontoxicity, high theoretical specific capacity (308 mAh g–1), and various crystal types (α-/β-/δ-/γ-MnO2). Unfortunately, their intrinsic shortcomings, including low conductivity and poor structural stability, lead to unsatisfactory electrochemical performance (poor rate performance and rapid capacity decay). Herein, a novel manganese dioxide cathode material with oxygen vacancies and a heterophase homostructure was designed and produced by a one-step hydrothermal process. This unique design could enhance conductivity and accelerate electron transfer. As expected, AZIBs showed excellent cycle performance with a capacity decay rate of 0.014% per cycle during 2800 cycles as well as outstanding rate performance (76.6 mAh g–1 at 10 A g–1). Furthermore, AZICs offer an energy density of 48.8 Wh kg–1 at a power density of 100 W kg–1 and a capacity retention rate of up to 73.4% even after 10,000 cycles. These discoveries pave the way for the rational design of high-performance electrode materials and provide an innovative option for next-generation energy storage systems.

Abstract The ubiquitous nature of amines in drug compounds, bioactive molecules and natural products has fueled intense interest in their synthesis. Herein, we introduce a nickel‐catalyzed enantioconvergent allenylic amination of methanol‐activated allenols. This protocol affords a diverse array of functionalized allenylic amines in high yields and with excellent enantioselectivities. The synthetic potential of this method is demonstrated by employing bioactive amines as nucleophiles and conducting gram‐scale reactions. Furthermore, mechanistic investigations and DFT calculations elucidate the role of methanol as an activator in the nickel‐catalyzed reaction, facilitating the oxidative addition of the C−O bond of allenols through hydrogen‐bonding interactions. The remarkable outcomes arise from a rapid racemization of allenols enabled by the nickel catalyst and from highly enantioselective dynamic kinetic asymmetric transformation of η 3 ‐alkadienylnickel intermediates.