Enantioselective Total Synthesis of (+)-Psiguadial B

The first enantioselective total synthesis of the cytotoxic natural product (+)-psiguadial B is reported. Key features of the synthesis include (1) the enantioselective preparation of a key cyclobutane intermediate by a tandem Wolff rearrangement/asymmetric ketene addition, (2) a directed C(sp^3)–H alkenylation reaction to strategically forge the C1–C2 bond, and (3) a ring-closing metathesis to build the bridging bicyclo[4.3.1]decane terpene framework

A modular approach to prepare enantioenriched cyclobutanes: synthesis of (+)-rumphellaone A

A modular synthesis of enantioenriched polyfunctionalized cyclobutanes was developed that features an 8-aminoquinolinamide directed C–H arylation reaction. The C–H arylation products were derivatized through subsequent decarboxylative coupling processes. This synthetic strategy enabled a 9-step enantioselective total synthesis of the antiproliferative meroterpenoid (+)-rumphellaone A

Hypoxia drives plastic divergence in cichlid body shape.

Abstract Organisms experience multiple selective agents that can influence phenotypes through heritable and/or plastic changes, often reflecting complex interactions between phenotype and environment. Environmental factors can directly influence phenotypes, but also indirectly affect phenotypic variation when genetic/plastic change in one trait results in correlated genetic/plastic change in another trait. In fishes, body shape is a trait that might be particularly prone to influence from environmental pressures that act on other morphological features. Variation in dissolved oxygen among aquatic environments has a large impact on the size of the gills and brains of fishes. It is likely that dissolved oxygen interacts with other environmental factors to both directly and indirectly influence patterns of body shape variation. We examined effects of dissolved oxygen on body shape variation among populations of an African cichlid fish (Pseudocrenilabrus multicolor) from multiple high-and low-oxygen sites within a single drainage in Uganda. A split-brood laboratory experiment was used to estimate plasticity of gill and brain size, and we used morphometric analyses to identify variation in body shape in F 1 offspring. Several analyses enabled us to identify genetic effects among populations, and effects of oxygen acting either directly on body shape or indirectly through its effects on gill and brain size. A large part of the variation in body shape was due to plastic variation in gill size associated with dissolved oxygen. Fish raised under low oxygen had deeper heads and shorter bodies, and this variation was driven by both direct effects of oxygen and indirect effects of gill size variation. Body shape variation in fishes should reflect interacting effects of multiple environmental factors that act directly or indirectly on morphology. Body shape might be particularly difficult to predict when phenotypes are plastic, because changes among populations would occur rapidly and be unrelated to genetic variation

A modular approach to prepare enantioenriched cyclobutanes: synthesis of (+)-rumphellaone A

A modular synthesis of enantioenriched polyfunctionalized cyclobutanes was developed that features an 8-aminoquinolinamide directed C–H arylation reaction. The C–H arylation products were derivatized through subsequent decarboxylative coupling processes. This synthetic strategy enabled a 9-step enantioselective total synthesis of the antiproliferative meroterpenoid (+)-rumphellaone A

Evolution of a Strategy for the Enantioselective Total Synthesis of (+)-Psiguadial B

(+)-Psiguadial B is a diformyl phloroglucinol meroterpenoid that exhibits antiproliferative activity against the HepG2 human hepatoma cancer cell line. This full account details the evolution of a strategy that culminated in the first enantioselective total synthesis of (+)-psiguadial B. A key feature of the synthesis is the construction of the trans-cyclobutane motif by a Wolff rearrangement with in situ catalytic, asymmetric trapping of the ketene. An investigation of the substrate scope of this method to prepare enantioenriched 8-aminoquinolinamides is disclosed. Three routes toward (+)-psiguadial B were evaluated that featured the following key steps: (1) an ortho-quinone methide hetero-Diels–Alder cycloaddition to prepare the chroman framework, (2) a Prins cyclization to form the bridging bicyclo[4.3.1]decane system, and (3) a modified Norrish–Yang cyclization to generate the chroman. Ultimately, the successful strategy employed a ring-closing metathesis to form the seven-membered ring and an intramolecular O-arylation reaction to complete the polycyclic framework of the natural product

A novel antigen capture ELISA for the specific detection of IgG antibodies to elephant endotheliotropic herpes virus

BACKGROUND Elephants are classified as critically endangered animals by the International Union for Conservation of Species (IUCN). Elephant endotheliotropic herpesvirus (EEHV) poses a large threat to breeding programs of captive Asian elephants by causing fatal haemorrhagic disease. EEHV infection is detected by PCR in samples from both clinically ill and asymptomatic elephants with an active infection, whereas latent carriers can be distinguished exclusively via serological assays. To date, identification of latent carriers has been challenging, since there are no serological assays capable of detecting seropositive elephants. RESULTS Here we describe a novel ELISA that specifically detects EEHV antibodies circulating in Asian elephant plasma/serum. Approximately 80 % of PCR positive elephants display EEHV-specific antibodies. Monitoring three Asian elephant herds from European zoos revealed that the serostatus of elephants within a herd varied from non-detectable to high titers. The antibody titers showed typical herpes-like rise-and-fall patterns in time which occur in all seropositive animals in the herd more or less simultaneously. CONCLUSIONS This study shows that the developed ELISA is suitable to detect antibodies specific to EEHV. It allows study of EEHV seroprevalence in Asian elephants. Results confirm that EEHV prevalence among Asian elephants (whether captive-born or wild-caught) is high