Collective Synthesis of Illudalane Sesquiterpenes via Cascade Inverse Electron Demand (4 + 2) Cycloadditions of Thiophene S,S-Dioxides.

Thiophene S,S-dioxides are underutilized tools for the de novo construction of benzene rings in organic synthesis. We report a collective synthesis of nine illudalane sesquiterpenes using bicyclic thiophene S,S-dioxides as generalized precursors to the indane core of the natural products. Exploiting furans as unusual dienophiles in this inverse electron demand Diels-Alder cascade, this concise and convergent approach enables the synthesis of these targets in as little as five steps. Theoretical studies rationalize the reactivity of thiophene S,S-dioxides with both electron-poor and electron-rich dienophiles and reveal reaction pathways involving either nonpolar pericyclic or bifurcating ambimodal cycloadditions. Overall, this work demonstrates the wider potential of thiophene S,S-dioxides as convenient and flexible precursors to polysubstituted arenes.

Late-stage and strain-accelerated oxidation enabled synthesis of haouamine A.

Herein we report a new synthetic entry to the strained cyclophane alkaloid natural product, haouamine A. The successful strategy featured a rhodium-catalyzed diazo-insertion reaction to install the all-carbon quaternary center and a rhodium-catalyzed intramolecular aziridination reaction to establish the nitrogen-bearing stereocenter, of the target molecule. Most notably, a late-stage, site-selective and strain-accelerated oxidation of a "deoxygenated" macrocyclic intermediate was successfully implemented, and in doing so provided a novel solution to the infamous biphenol cyclophane system of haouamine A.

A desymmetrization-based approach to morphinans: application in the total synthesis of oxycodone.

Here we report a total synthesis of the pharmacologically significant morphinan alkaloid, oxycodone. The centerpiece of the developed strategy features the first application of the Rovis desymmetrization of peroxyquinol in target-oriented total synthesis to access an optically active phenanthrene framework shared by the morphinans. A Stork-Ueno radical cyclization under photoredox conditions installed the all-carbon quaternary stereocenter, and a late-stage reductive detosylation with concomitant piperidine formation secured the core structure of the target molecule.

Mixture risk assessment of selected mainstream cigarette smoke constituents generated from low-yield cigarettes in South Korean smokers.

A total of 38 hazardous constituents in mainstream cigarette smoke of low-yield cigarettes sold in Korea were selected and analyzed using established methods. Risk calculations were performed using risk algorithms employed in previous studies and Korean population-based exposure parameters. The median cumulative incremental lifetime cancer risk of male smokers could vary from 828 × 10-6 to 2510 × 10-6, and that of female smokers could range from 440 × 10-6 to 1300 × 10-6, depending on the smoking regimens. The median hazard index as the sum of hazard quotients of male smokers varied from 367 to 1,225, and that of female smokers varied from 289 to 970, depending on the smoking regimens. The sensitivity analysis for this risk assessment indicated that the constituent yields in mainstream cigarette smoke, average number of cigarettes smoked per day or year, and mouth-spill rate are the main risk factors. Statistical positive correlations between the average daily dose calculated by the exposure algorithm used in this study for individual smokers and biomarkers verified the reliability of this assessment. It could be concluded that inhalation of the constituents present in the mainstream of low-yield cigarettes has significant cancer and non-cancer health risks, although its effect on risk reduction is still unknown under the fixed machine-smoking conditions.

Heterogeneous photocatalysis of aromatic and chlorinated volatile organic compounds (VOCs) for non-occupational indoor air application.

The current study evaluated the technical feasibility of applying TiO2 photocatalysis to the removal of low-ppb concentrations of volatile organic compounds (VOCs) commonly associated with non-occupational indoor air quality issues. A series of experiments was conducted to evaluate five parameters (relative humidity (RH), hydraulic diameter (HD), feeding type (FT) for VOCs, photocatalytic oxidation (PCO) reactor material (RM), and inlet port size (IPS) of PCO reactor) in relation to the PCO destruction efficiencies of the selected target VOCs. None of the target VOCs exhibited any significant dependence on the RH, which is inconsistent with a previous study where, under conditions of low humidity and a ppm toluene inlet level, a drop in the PCO efficiency was reported with a decreasing humidity. However, the other four parameters (HD, RM, FT, and IPS) were found to be important for better VOC removal efficiencies as regards the application of TiO2 photocatalytic technology for cleansing non-occupational indoor air. The PCO destruction of VOCs at concentrations associated with non-occupational indoor air quality issues was up to nearly 100%, and the CO generated during PCO was a negligible addition to indoor CO levels. Accordingly, a PCO reactor would appear to be an important tool in the effort to improve non-occupational indoor air quality.

Comparison of outdoor and indoor mobile source-related volatile organic compounds between low- and high-floor apartments.

The current study examined the hypothesis that there may be vertical variation in mobile source-related volatile organic compound (VOC) concentrations in high-rise apartment buildings. One hundred twelve homes in 56 high-rise apartment buildings with 10 or more stories participated in the study. Both the outdoor and the indoor air concentrations of three VOCs [methyl-tertiary butyl ether (MTBE), benzene, and toluene] were significantly higher for the low-floor apartments than for the high-floor apartments (P < 0.05). The median outdoor concentrations were 5.4, 6.8, and 29.1 microgram/m3, respectively, for the low-floor apartments, yet 4.4, 4.3, and 21.9 microgram/m3, respectively, for the high-floor apartments. Meanwhile, the median indoor concentrations were 6.3, 9.4, and 44.8 microgram/m3, respectively, for the low-floor apartments, yet 5.1, 7.6, and 38.8 microgram/m3, respectively, for the high-floor apartments. These findings indicate that residents of low-floor apartments are exposed to elevated residential levels of mobile source-related VOCs compared to high-floor apartment residents. The indoor concentrations of the target VOCs, except for MTBE, were significantly higher than the outdoor air concentrations for both the low and high floors (P < 0.05). Plus, the outdoor and indoor VOC concentrations were significantly different between the daytime and nighttime data sets for both low- and high-floor apartments, with a P value of less than or close to 0.05.