The merger of electrochemistry and transition metal catalysis has emerged as a powerful tool to join two electrophiles in an enantioselective manner. However, the development of enantioselective electroreductive cross-couplings of olefins remains a challenge. Inspired by the advantages of the synergistic use of electrochemistry with nickel catalysis, we present here a Ni-catalyzed enantioselective electroreductive cross-coupling of acrylates with aryl halides and alkyl bromides, which affords chiral α-aryl carbonyls in good to excellent enantioselectivity. Additionally, this catalytic reaction can be applied to (hetero)aryl chlorides, which is difficult to achieve by other methods. The combination of cyclic voltammetry analysis with electrode potential studies suggests that the NiI species activates aryl halides by oxidative addition and alkyl bromides by single-electron transfer.
Metal-catalyzed asymmetric electro-reductive couplings have emerged as a powerful tool for organic synthesis, wherein a sacrificial anode is typically required. Herein, a parallel paired electrolysis (PPE)-enabled asymmetric catalysis has been developed, and the alcohols and ketones could be simultaneously converted to the corresponding aldehydes and chiral tertiary alcohols with high yields and enantioselectivity in an undivided cell. Additionally, this Ni-catalyzed asymmetric reductive coupling can well match the anodic oxidative C-H bond bromination of (hetero)arenes. This protocol opens an alternative avenue for organic synthesis.
Here, we report an asymmetric electrochemical organonickel-catalyzed reductive cross-coupling of aryl aziridines with aryl iodides in an undivided cell, affording ß-phenethylamines in good to excellent enantioselectivity with broad functional group tolerance. The combination of cyclic voltammetry analysis of the catalyst reduction potential as well as an electrode potential study provides a convenient route for reaction optimization. Overall, the high efficiency of this method is credited to the electroreduction-mediated turnover of the nickel catalyst instead of a metal reductant-mediated turnover. Mechanistic studies suggest a radical pathway is involved in the ring opening of aziridines. The statistical analysis serves to compare the different design requirements for photochemically and electrochemically mediated reactions under this type of mechanistic manifold.
A scalable enantioselective nickel-catalyzed electrochemical reductive homocoupling of aryl bromides has been developed, affording enantioenriched axially chiral biaryls in good yield under mild conditions using electricity as a reductant in an undivided cell. Common metal reductants such as Mn or Zn powder resulted in significantly lower yields in the absence of electric current under otherwise identical conditions, underscoring the enhanced reactivity provided by the combination of transition metal catalysis and electrochemistry.
We have studied the effect of geometry deformation on the mechanical frequencies and quality factors for different modes in the Whispering Gallery Mode (WGM) microresonators, that is unavoidable in the practical fabrication. The subsidence of the sphere and a more general condition with fewer symmetries and complex deformation of eccentricity, subsidence, and offset are first modeled in this paper, which could tune the mechanical frequency in a much wider spectral range than the pillar-diameter-induced perturbation. we also show that the mechanical quality factors for the non-whispering-gallery mechanical mode could be increased in the order of 4 magnitudes at a specific subsidence, and form a mechanical bound state in the continuum (BIC) which is induced by the symmetry breaking and reveals new mechanisms to confine radiation. A much broader BIC window width with higher mechanical quality factor could be achieved, which is of great importance in both fundamental research and scientific applications.
