8-Membered-ring Transition States of Water Assisted Reactions in Sub-and Super-critical Water

1 Results Sub-and super-critical water is an attractive reaction medium for organic transformation because of their unique properties such as low viscosity,high density,low polarity,high solubility to organic compounds,and,of course,the greenness of the medium[1-3]. We report herein some unique reactions of unsaturated compounds in sub-and super-critical water.When allylbenzene was treated in supercritical water (SCW: 380 ℃,10 min,water density=0.35 g/mL),double bond migrated to give a mixture of allylb...

High-purity helical carbon nanotubes by trace-water- assisted chemical vapor deposition： Large-scale synthesis and growth mechanism

Helical carbon nanotubes （HCNTs） are highly desirable due to their unique geometrical elegance and inherent physical properties; however, high-efficiency synthesis of high-purity HCNTs with high yield and full elucidation of their growth mechanism remains challenging. Traditional methods to achieve the high-yield growth of HCNTs mainly focus on controlling the size of catalytic particles. Herein, we found that addition of trace water greatly benefits large-scale synthesis of HCNTs. Uniform HCNTs with - 100% purity can be obtained, and the yield of HCNTs can reach ~ 8,078% in a run of 6 h, much higher than that obtained without trace water and any of the reported yields. Experiments and theoretical simulations are performed to reveal that the trace water can react with the dangling bond on carbon, thus inhibiting the generation of amorphous species. Furthermore, the trace water can enhance the anisotropy of the catalyst surface. This results in different segregation rates of carbon atoms coming out of different crystal planes and further periodic mismatch of the graphite layers, thus leading to the formation of HCNTs. Therefore, this new and efficient method is promising for practical, large-scale production of HCNTs.

Asymmetric catalytic alkylation of vinyl azides with 3-bromo oxindoles: water-assisted chemo-and enantiocontrol

A highly chemo-and enantioselective alkylation of vinyl azides with 3-bromo-3-substituted oxindoles was achieved through a chiral N,N′-dioxide/Ni(OTf)2-mediated conjugate addition/water addition/elimination tandem process. Water was critical to the chemo-and enantioselectivity. The hydrated Na3PO4 acted as both a base and a reservoir to regulate the amount of water in solution. A wide range of enantioenriched oxindoles having α-carbonyl-substituted all-carbon quaternary stereocenters were achieved in good yields and good ee values(51 examples, up to 90% yield, 97% ee). Easy transformations of products to analogues of(+)-physovenine and(+)-desoxyeseroline enhanced the synthetic value. Mechanistic studies including control experiments, kinetic studies, and density functional theory(DFT) calculations, enabled a proposition of a possible catalytic cycle along with transition states to elucidate the reaction process and chiral induction.