2021, Xua, Jian-Xing, Wu, Fu-Peng, Wu, Xiao-Feng

Herein, we developed a rhodium-catalyzed reduction of CO with bis(pinacolato)diboron (B2pin2) under atmospheric pressure of CO with silane as the hydride source, gem-diborylmethane [H2C(Bpin)2] as a versatile and fundamental C1 compound can be formed. Notably, this is the first example on transition metal-catalyzed borylation of CO. © 2020 The Author(s)

2021, Yuan, Yang, Wu, Fu-Peng, Spannenberg, Anke, Wu, Xiao-Feng

Functionalized bisboryl compounds have recently emerged as a new class of synthetically useful building blocks in organic synthesis. Herein, we report an efficient strategy to synthesize β-geminal-diboryl ketones enabled by a Cu/Pd-catalyzed borocarbonylative trifunctionalization of readily available alkynes and allenes. This reaction promises to be a useful method for the synthesis of functionalized β-geminal-diboryl ketones with broad functional group tolerance. Mechanistic studies suggest that the reaction proceeds through borocarbonylation/hydroboration cascade of both alkynes and allenes.

2021, Xu, Tiefeng, Lu, Panting, Wohlrab, Sebastian, Chen, Wenxing, Springer, Armin, Wu, Xiao-Feng, Lu, Wangyang

Palladium nanoparticles supported on low-melting polyester (Pd/LMPET) fabric were prepared through a microwave irradiation assisted method. In this way, in situ growth of Pd nanoparticles onto an easy to handle material was initiated and proceeded. The results of the characterization revealed that the palladium nanoparticles were well-dispersed on the surfaces of the polyester fibers. The Pd/LMPET fabrics were then employed in the Suzuki-Miyaura coupling. They exhibited excellent catalytic activity in ethanol/water under air atmosphere at 50 °C. Importantly, the Pd/LMPET fabrics could be separated from reaction mixture conveniently and they can still maintain good activity after 8 cycles without Pd leaching. © 2021 The Authors

2021, Ai, Han-Jun, Ma, Xingxing, Song, Qiuling, Wu, Xiao-Feng

The unique properties of fluorine-containing organic compounds make fluorine substitution attractive for the development of pharmaceuticals and various specialty materials, which have inspired the evolution of diverse C-F bond activation techniques. Although many advances have been made in functionalizations of activated C-F bonds utilizing transition metal complexes, there are fewer approaches available for nonactivated C-F bonds due to the difficulty in oxidative addition of transition metals to the inert C-F bonds. In this regard, using Lewis acid to abstract the fluoride and light/radical initiator to generate the radical intermediate have emerged as powerful tools for activating those inert C-F bonds. Meanwhile, these transition-metal-free processes are greener, economical, and for the pharmaceutical industry, without heavy metal residues. This review provides an overview of recent C-F bond activations and functionalizations under transition-metal-free conditions. The key mechanisms involved are demonstrated and discussed in detail. Finally, a brief discussion on the existing limitations of this field and our perspective are presented.

2021, Wu, Fu-Peng, Wu, Xiao-Feng

The addition reaction between CuBpin and alkenes to give a terminal boron substituted intermediate is usually fast and facile. In this communication, a selectivity-reversed procedure has been designed and established. This selectivity-reversed borocarbonylation reaction is enabled by a cooperative action between palladium and copper catalysts and proceeds with complete regioselectivity. The key to the success of this transformation is the coordination of the amide group and slower CuBpin formation by using KHCO3as the base. A wide range of β-boryl ketones were produced from terminal unactivated aliphatic alkenes and aryl iodides. Further synthetic transformations of the obtained β-boryl ketones have been developed as well. © The Royal Society of Chemistry 2021.