ABSTRACT
We successfully employed bisphenol A and several different formyl-containing monomers as useful building blocks to construct a series of hydroxy-group-containing porous organic polymers in a sealed tube at high temperature. Fourier transform infrared and solid-state 13C CP/MAS NMR spectroscopy are utilized to characterize the possible structure of the obtained polymers. The highest Brunauer-Emmet-Teller specific surface area of the phenolic-resin porous organic polymers (PPOPs) is estimated to be 920 m2 g-1. The PPOPs exhibit a highest carbon dioxide uptake (up to 15.0 wt % (273 K) and 8.8 wt % (298 K) at 1.0 bar), and possess moderate hydrogen storage capacities ranging from 1.28 to 1.04 wt % (77 K) at 1.0 bar. Moreover, the highest uptake of methane for the PPOPs is measured as 4.3 wt % (273 K) at 1.0 bar.
ABSTRACT
4-Arylhexahydroindole derivatives 5 were synthesized from 2-arylcyclohexenyl allylamine derivatives 4, which have a large protecting group on nitrogen, using zirconium-promoted cyclization. Reaction of 4e with Cp(2)ZrBu(2), followed by treatment with MeMgBr and then O(2), gave 2a in 63% yield by a one-pot reaction, since the approach of O(2) to zirconium was prevented by the aryl group. The total syntheses of (+/-)-mesembrane and (+/-)-mesembrine were achieved starting from 2a. To synthesize these natural products in a chiral form, the starting allylamine derivative 24 (80% yield, 86% ee, recrystallized from MeOH, 99% ee with 79% recovery) was prepared from allyl carbonate 22a and N-tosylallylamine 23 using palladium-catalyzed asymmetric amination in the presence of (S)-BINAPO as a chiral ligand. (-)-Mesembrane and (-)-mesembrine were synthesized from this allylamine 24.