RESUMO
The utility of the dioxasiline ring as a π-facial directing group in the intramolecular Diels-Alder cyclization is explored. An initial investigation of substrate scope demonstrates that the rigidity of this directing group delivers robust stereocontrol across a number of substrates, affording single diastereomers in moderate to good yields. A mechanistic investigation reveals that the reactive diene is formed through γ deprotonation followed by [1,5] hydride shifts.
RESUMO
Osmium tetroxide and TMEDA form stable crystalline adducts with alkenes. The structure of liquid alkenes can be determined through the X-ray analysis of these derivatives. Osmium, a heavy atom, facilitates the crystallographic analysis and the determination of the absolute configuration using common Mo X-ray sources. The utility of this method for assigning structures and absolute configurations was demonstrated on a number of unsaturated substrates that include simple alkenes, enones, enol ethers, and silyl enol ethers.
RESUMO
A catalytic redox-neutral method for the synthesis of spirolactams proceeding through the dearomative spirocyclization of N-aryl alkynamides is reported. In contrast to stoichiometric activating agents employed for related transformations, we show that the use of 5 mol % of Au(PPh3)Cl and AgOTf in dichloroethane at 50-80 °C leads to selective spirocyclization, furnishing the products in yields of 35-87%. The substrate scope of the reaction is good, with both electron-donating and electron-withdrawing groups being tolerated around the arene ring, as well as substitution at the amide nitrogen. The identity of the para-alkoxy group on the arene ring is key to achieving selectivity for spirocyclization over alternative mechanistic pathways. While the presence of a para-methoxy group leads to trace amounts of the desired spirolactams, the para-tert-butoxy or para-hydroxy substrate analogues furnish the spirolactams in good yield with high selectivity.
RESUMO
We examined the response of demographic, morphological, and chemical parameters of turtle grass (Thalassia testudinum), to much-higher-than-normal rainfall associated with an El Niño event in the winter of 1997-1998. Up to 20 inches of added rain fell between December 1997 and March 1998. triggering widespread and persistent phytoplankton blooms along the west coast of Florida. Water-column chlorophyll concentrations estimated from serial Sea WiFS imagery were much higher during the El Niño event than in the previous or following years, although the timing and magnitude of phytoplankton blooms varied among sites. Seagrass samples collected in 1997, 1998, and 1999 provided an excellent opportunity to test the responsiveness of Thalassia to decline and subsequent improvement of water quality and clarity in four estuaries. Using a scoring technique based on temporal responsiveness, spatial consistency, and statistical strength of indicators, we found that several morphological parameters (Thalassia shoot density, blade width, blade number, and shoot-specific leaf area) were responsive and consistent measures of light stress. Some morphological parameters, such as rhizome apex density, responded to declines and subsequent improvement in water clarity, but lacked the statistical discriminating power necessary to be useful indicators. However, rhizome sugar, starch, and total carbohydrate concentrations also exhibited spatially and temporally consistent variation as well as statistical strength. Because changes in shoot density, as well as water clarity, affect rhizome carbohydrate levels, a composite metric based on Thalassia shoot density and rhizome carbohydrate levels together is probably more useful than either parameter alone as an indicator of seagrass health.
