A stereocontrolled total synthesis of the indole diterpenoid natural product paspaline is described. Key steps include a highly diastereoselective enzymatic desymmetrization, substrate-directed epoxidation, Ireland-Claisen rearrangement, and diastereotopic group selective C–H acetoxylation to assemble the target with excellent stereofidelity. The route and results described herein outline complementary conceptual disconnections in the arena of steroid natural product synthesis.

Abstract. Advances in air pollution sensor technology have enabled the development of small and low cost systems to measure outdoor air pollution. The deployment of a large number of sensors across a small geographic area would have potential benefits to supplement traditional monitoring networks with additional geographic and temporal measurement resolution, if the data quality were sufficient. To understand the capability of emerging air sensor technology, the Community Air Sensor Network (CAIRSENSE) project deployed low cost, continuous and commercially-available air pollution sensors at a regulatory air monitoring site and as a local sensor network over a surrounding ~ 2 km area in Southeastern U.S. Co-location of sensors measuring oxides of nitrogen, ozone, carbon monoxide, sulfur dioxide, and particles revealed highly variable performance, both in terms of comparison to a reference monitor as well as whether multiple identical sensors reproduced the same signal. Multiple ozone, nitrogen dioxide, and carbon monoxide sensors revealed low to very high correlation with a reference monitor, with Pearson sample correlation coefficient (r) ranging from 0.39 to 0.97, −0.25 to 0.76, −0.40 to 0.82, respectively. The only sulfur dioxide sensor tested revealed no correlation (r  0.5), step-wise multiple linear regression was performed to determine if ambient temperature, relative humidity (RH), or age of the sensor in sampling days could be used in a correction algorithm to improve the agreement. Maximum improvement in agreement with a reference, incorporating all factors, was observed for an NO2 sensor (multiple correlation coefficient R2adj-orig = 0.57, R2adj-final = 0.81); however, other sensors showed no apparent improvement in agreement. A four-node sensor network was successfully able to capture ozone (2 nodes) and PM (4 nodes) data for an 8 month period of time and show expected diurnal concentration patterns, as well as potential ozone titration due to near-by traffic emissions. Overall, this study demonstrates a straightforward methodology for establishing low-cost air quality sensor performance in a real-world setting and demonstrates the feasibility of deploying a local sensor network to measure ambient air quality trends.

Medicinal application of many complex natural products is precluded by the impracticality of their chemical synthesis. Pactamycin, the most structurally-intricate aminocyclopentitol antibiotic, displays potent anti-prolific properties across multiple phylogenetic domains, but is highly cytotoxic. A limited number of analogs produced by genetic engineering technologies show reduced cytotoxicity against mammalian cells, renewing promise for therapeutic applications. For decades, an efficient synthesis of pactamycin amenable to analog derivatizations has eluded researchers. Herein, we present a short asymmetric total synthesis of pactamycin. An enantioselective Mannich reaction/symmetry-breaking reduction sequence was designed to enable assembly of the entire carbon core skeleton in under five steps and control critical three-dimensional (stereochemical) functional group relationships. This modular route totals fifteen steps and is immediately amenable for structural analog synthesis.

An enantioselective synthesis of the indole diterpenoid natural product paspaline is disclosed. Critical to this approach was the implementation of stereoselective desymmetrization reactions to assemble key stereocenters of the molecule. The design and execution of these tactics are described in detail, and a thorough analysis of observed outcomes is presented, ultimately providing the title compound in high stereopurity. This synthesis provides a novel template for preparing key stereocenters in this family of molecules, and the reactions developed en route to paspaline present a series of new synthetic disconnections in preparing steroidal natural products.

An asymmetric total synthesis of the aminocyclopentitol pactamycin is described, which delivers the title compound in 15 steps from 2,4-pentanedione. Critical to this approach was the exploitation of a complex symmetry-breaking reduction strategy to assemble the C1, C2, and C7 relative stereochemistry within the first four steps of the synthesis. Multiple iterations of this reduction strategy are described, and a thorough analysis of stereochemical outcomes is detailed. In the final case, an asymmetric Mannich reaction was developed to install a protected amine directly at the C2 position. Symmetry-breaking reduction of this material gave way to a remarkable series of stereochemical outcomes leading to the title compound without recourse to non-strategic downstream manipulations. This synthesis is immediately accommodating to the facile preparation of structural analogs.

Benzenoids in principle represent attractive and abundant starting materials for the preparation of substituted cyclohexanes; however, the synthetic tools available for overcoming the considerable aromatic energies inherent to these building blocks limit the available product types. In this paper, we demonstrate access to heretofore unknown heterotricyclic structures by leveraging oxidative dearomatization of 2-hydroxymethyl phenols with concurrent N-hydroxycarbamate dehydrogenation using a common oxidant. The pairwise-generated, mutually reactive species then participate in a second stage acylnitroso Diels–Alder cycloaddition. The reaction chemistry of the derived [2.2.2]-oxazabicycles, bearing four orthogonal functional groups and three stereogenic centers, is shown to yield considerable diversity in downstream products. The methodology allows for the expeditious synthesis of a functionalized intermediate bearing structural and stereochemical features in common with the complex alkaloid tetrodotoxin.

In early 2009 the Planets project undertook a survey of national libraries, archives, and other content-holding organisations in Europe to better understand the organisations' digital preservation activities and needs, and to ensure that Planets' technology and services are designed to meet them. Over 200 responses were received including a cross-section of major libraries and archives especially in Europe. The results provide a snapshot of organisations' readiness to preserve digital collections for the future. The survey revealed a high level of awareness of the challenges of digital preservation within organisations. Findings indicated that approximately half of those organisations surveyed have taken measures to develop digital preservation policies and to budget for it, while a majority have incorporated digital preservation into their organisational planning. Organisations predict that within a decade they will need to store large quantities of data in a wide range of formats from a variety of sources; three quarters of them are looking to invest in a solution within the next two years. However, the findings also point to varying degrees of readiness. Organisations with a digital preservation policy are significantly further advanced in their work to preserve digital collections for the long-term than others.

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