ABSTRACT
In this study, ground granulated blast furnace slag was activated with a wide variety of sodium salts to compare the effects of their pH and anion size on the hydration progress and compressive strength development of GGBFS pastes. Research was carried out on samples activated with twelve different sodium salts and cured for one year. Changes in their phase composition (XRD), loss on ignition at different temperatures, expansion and microstructure (SEM + EDS) were examined over the entire curing period. The results showed that the presence of sodium ions is more important than the pH of the system, as activation took place even in the case of compounds whose solutions are characterized by a low pH, such as sodium tartrate or phosphate. The compressive strength of the pastes ranged from approximately 8 to 65 MPa after one year of curing.
ABSTRACT
The synthesis of polyhydroxylated 2-allylpyrrolidines from sugar-derived bromonitriles in a cascade addition of allylmagnesium bromide/SN2 cyclization/reduction with Zn(BH4)2 is described. The stereochemical course of the reduction step is rationalized. Two of the obtained compounds are transformed into stereoisomers of naturally-occurring iminosugar (+)-lentiginosine. In an alternative approach, 2,2-diallylpyrrolidines are obtained from bromonitriles in a cascade addition of allylmagnesium bromide/SN2 cyclization/addition of another equivalent of allylmagnesium bromide.
Subject(s)
Carbohydrates/chemistry , Nitriles/chemistry , Organometallic Compounds/chemistry , Pyrrolidines/chemical synthesis , Allyl Compounds/chemistry , Bromides/chemistry , Cyclization , Magnesium Compounds/chemistry , Molecular Conformation , Oxidation-Reduction , Pyrrolidines/chemistry , StereoisomerismABSTRACT
Synthesis of novel polyhydroxylated derivatives of decalin is described. The presented methodology consists in a one-pot copper-catalyzed 1,4-addition of vinylmagnesium bromide to sugar-derived cyclohexenone, followed by an aldol reaction with a derivative of but-3-enal. The obtained diene is then subjected to an assisted tandem catalytic sequence: ring-closing metathesis with the subsequent reuse of the Ru-catalyst in the syn-dihydroxylation. The stereochemical outcome of these reactions is discussed.
ABSTRACT
The first palladium-mediated C-H allylic oxidation with a Cbz group acting as an O-nucleophile is reported. It was found that this transformation is promoted by rare-earth metal triflates: Yb(OTf)(3) or Sc(OTf)(3). A possible catalytic cycle is proposed. This reaction was applied in the synthesis of a d-xylose derived oxazolidinon, a versatile intermediate used further in the stereoselective synthesis of unnatural (-)-castanospermine. Cyclization of the key intermediate with PhSeBr afforded the desired bicyclic scaffold. In an alternative route, hydroboration/oxidation followed by DPPA-mediated cyclization was used.
Subject(s)
Indolizines/chemical synthesis , Xylose/chemistry , Azides/chemistry , Catalysis , Cyclization , Indolizines/chemistry , Molecular Structure , Palladium , Stereoisomerism , Xylose/chemical synthesisABSTRACT
The synthesis of novel polyhydroxylated quinolizidines and azaspiro[4.5]decanes is reported. A key step of this transformation involved an addition of allylmagnesium bromide to an ω-bromonitrile derived from D-xylose followed by an intramolecular displacement of a bromide. The resulting cyclic imine was treated either with allylmagnesium bromide or with NaBH4, to provide 2,2-diallyl- or 2-allylpiperidine, respectively. The desired bicyclic framework was constructed via a ring-closing metathesis reaction. The Ru catalysts were reused in the following syn-dihydroxylation step.
