Palladium-Catalyzed Norbornene-Mediated Tandem Amination/Cyanation Reaction: A Method for the Synthesis of <i>ortho</i>-Aminated Benzonitriles

A palladium-catalyzed, norbornene-mediated tandem amination/cyanation reaction via Catellani-type C–H functionalization was developed using <i>N</i>-benzoyloxyamines as the amination reagent and Zn­(CN)₂ as the terminating agent. This transformation, in which one C–N bond and one C–C bond are formed, provides an efficient approach for the synthesis of <i>ortho</i>-aminated benzonitriles in one pot from easily accessible starting materials

Scatterplot of behavioral response profiles of juveniles (blue dots) and adults (red dots) within two-dimensional canonical space.

<p>Groups that are significantly different tend to have non-intersecting ellipses, in this case suggesting significant differences between juveniles and adults. See <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0132817#pone.0132817.g005" target="_blank">Fig 5</a> for details on the meaning of plot symbols.</p

<i>K</i>-means cluster plot showing different behavioral approaches adopted (for coping with life-threatening distress experienced by an individual) within multivariate decision space.

<p>Plot is of points and clusters in the first two principal components. Circles are drawn around the cluster centers. The sizes of the circle outlines are proportional to the count inside the cluster. The shaded areas are the 90% density contour around the mean, indicating where 90% of the observations in that cluster would fall. Data values belonging to each cluster are indicated by different colored symbols. Behavioral classification was based upon examination of coordinate plots characterizing each cluster. Ray plot in the middle indicates contribution of each parameter. Biting, distress and freezing behaviors were roughly equally weighted and showed orthogonal mapping within the plot.</p

Supplementary material

The raw data and alternative linear mixed models are listed in the tables. The video is recorded via an infrared camera (SonyHDR- CX760PJ760, Japan) in the in temporary field station near the bat roost

Scatterplot of behavioral response profiles of juveniles (blue dots) and adults (red dots) within two-dimensional canonical space.

<p>Groups that are significantly different tend to have non-intersecting ellipses, in this case suggesting significant differences between juveniles and adults. See <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0132817#pone.0132817.g005" target="_blank">Fig 5</a> for details on the meaning of plot symbols.</p

Comparisons of escape behavior of big-footed myotis between adults and juveniles during three contexts.

<p>N₁ refers to the number of adult bats.</p><p>N₂ refers to the number of juvenile bats.</p><p>Statistically significant results are highlighted in bold.</p><p>‘-’ indicates that big-footed myotis didn’t emit distress calls during predator threat. The differences in escape response between adults and juveniles were compared using Independent-Sample T test or Mann-Whitney U test.</p><p>^a These statistical analyses were performed with Fisher's exact test, thus, there was not test value given.</p><p>Comparisons of escape behavior of big-footed myotis between adults and juveniles during three contexts.</p

Escape behavior of big-footed myotis both in adults (N = 54) and juveniles (N = 28) during three contexts.

<p>^a Data are presented as Mean ± SE.</p><p>^b Data are presented as percentage.</p><p>‘0’ indicates that big-footed myotis didn’t emit distress calls during predator threat.</p><p>Escape behavior of big-footed myotis both in adults (N = 54) and juveniles (N = 28) during three contexts.</p

Schematic of experimental setup.

<p>Bats were trapped in mist-nets. An infrared digital video camera monitored the behavior of trapped bats. Three condenser microphones (Avisoft Bioacoustics CM16/CMPA) synchronously recorded the calls of trapped bats in different directions, microphone 4 recorded the calls of other bats in cave. All microphones connected with an ultrasonic acquisition system, and all calls were recorded onto a Dell Latitude laptop.</p

Scatterplot of behavioral response profiles of juveniles and adults within two-dimensional canonical space for environmental distress (green dots), predator distress (blue dots) and arrest (red dots).

<p>Variable direction rays are placed within the plot. The "+" symbols indicate the location of the multivariate mean. The canonical plot shows the points and multivariate means in the two dimensions that best separate the groups. The size of the inner ellipse corresponds to a 95% CL for the mean. Groups that are significantly different tend to have non-intersecting ellipses, in this case suggesting significant differences among the three life-threatening distressful situations encountered by the bats. The outer ellipses show areas that contain roughly 50% of the points for that group.</p

Data_Sheet_1_Correlated evolution of wing morphology and echolocation calls in bats.DOCX

IntroductionFlight and echolocation are two crucial behaviors associated with niche expansion in bats. Previous researches have attempted to explain the interspecific divergence in flight morphology and echolocation vocalizations in some bat groups from the perspective of foraging ecology. However, the relationship between wing morphology and echolocation vocalizations of bats remains obscure, especially in a phylogenetic context.ObjectivesHere, we aimed to assess the correlated evolution of wing morphology and echolocation calls in bats within a phylogenetic comparative framework.MethodsWe integrated the information on search-phrase echolocation call duration, peak frequency, relative wing loading, aspect ratio, and foraging guilds for 152 bat species belonging to 15 families. We quantified the association among wing morphology, echolocation call parameters, and foraging guilds using phylogeny-based comparative analyses.ResultsOur analyses revealed that wing morphology and echolocation call parameters depended on families and exhibited a marked phylogenetic signal. Peak frequency of the call was negatively correlated with relative wing loading and aspect ratio. Call duration was positively correlated with relative wing loading and aspect ratio among open-space aerial foragers, edge-space aerial foragers, edge-space trawling foragers, and narrow-space gleaning foragers. Wing morphology, call duration, and peak frequency were predicted by foraging guilds.ConclusionThese results demonstrate that adaptive response to foraging ecology has shaped the correlated evolution between flight morphology and echolocation calls in bats. Our findings expand the current knowledge regarding the link between morphology and vocalizations within the order Chiroptera.</p