The catalytic asymmetric Mannich/condensation of glycine ester with aldimines was achieved by merging chiralN,N′-dioxide/YbIIIcomplex Lewis acid catalysis/carbonyl catalysis under mild condition.
A highly enantioselective [2+2] cycloaddition reaction of alkylidene malonates with the internal CC bond of N-allenamides was developed with a MgII/N,N′-dioxide complex as a catalyst. Various polysubstituted methylenecyclobutanes were afforded in good yields (up to 99%) and excellent enantioselectivities (up to 96% ee) under mild conditions. The utility of the donor–acceptor cyclobutane product was demonstrated as a masked 1,4-dipole in the formal [4+2] annulation reaction with a silyl enol ether.
A catalytic asymmetric conjugate addition/Schmidt-type rearrangement of vinyl azides and (E)-alkenyloxindoles was realized. It afforded a variety of optically active 3,2′-pyrrolinyl spirooxindoles with high yields (up to 98%), and excellent diastereo- and enantioselectivities (up to 98% ee, >19 : 1 dr), even at the gram-scale in the presence of a chiral N,N′-dioxide–nickel(II) complex. In addition, a possible catalytic cycle and transition state model were proposed to rationalize the stereoselectivity.
The asymmetric synthesis of enantioenriched C3-arylated oxindoles bearing a tetrasubstituted stereocenter has been achieved using a chiral N,N′-dioxide/transition metal complex which promoted the Friedel–Crafts alkylation of 3-bromo-3-substituted oxindoles with arenes and heteroarenes, i.e., anisole derivatives, furans, pyrroles, 2-methoxythiophene, anilines, and phenols. A series of 3-aryl-indolinones with quaternary stereocenters have been obtained in up to 99% yields and 99% ee. In addition, the rationale for the reactivity is based on the nucleophilicity parameters of arenes and heteroarenes, which were predicted from Mayr's Database. Also, a gram-scale synthesis has been achieved and this method has been applied to the synthesis of bioactive compounds. Additionally, a plausible catalytic cycle has been proposed.
We have synthesized β-diaryl-β-hydroxyl-α-amino acid derivatives through radical addition-type aldol reaction, which was confirmed by spectroscopic experiments, control experiments, and DFT calculations.
4 July 2017 in Journal of Essential Oil Bearing Plants
A comparative analysis of chemical compounds found in essential oil and ethanol extract from Rhododendron tomentosum Harmaja was conducted in this study. The major volatile components were identified as 4-thujene (27.05%), α-thujenal (12.24%), and (-)-4-terpineol (9.78%) in the essential oil. The contents of total flavonoids and total phenolics in the raw material were 37.9 mg rutin equivalent/g and 4.2 mg gallic acid equivalent/g dry matter, respectively; the contents of ursolic acid, hyperoside, quercetin, and kaempferol were 15.2, 1.29, 0.32, and 0.03 mg/g, respectively. The volatile components in ethanol extract contained α-farnesene (8.35%), n-tetradecane (6.37%), hexadecanoic acid (6.14%), oblivon c (5.89%), and lilac aldehyde (4.85%). Ethanol extract exhibited higher antioxidant capacities than essential oil, which were evaluated by DPPH assay and ABTS assay.