Enantioselective Construction of Acyclic Quaternary Carbon Stereocenters: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully-Substituted Amide Enolates

We report a divergent and modular protocol for the preparation of acyclic molecular frameworks containing newly created quaternary carbon stereocenters. Central to this approach is a sequence composed of a (1) regioselective and -retentive preparation of allyloxycarbonyl-trapped fully substituted stereodefined amide enolates and of a (2) enantioselective palladium-catalyzed decarboxylative allylic alkylation reaction using a novel bisphosphine ligand

Probing Trends in Enantioinduction via Substrate Design: Palladium-Catalyzed Decarboxylative Allylic Alkylation of α-Enaminones

Herein, we report the palladium-catalyzed decarboxylative asymmetric allylic alkylation of α-enaminones. In addition to serving as valuable synthetic building blocks, we exploit the α-enaminone scaffold and its derivatives as probes to highlight structural and electronic factors that govern enantioselectivity in this asymmetric alkylation reaction. Utilizing the (S)-t-BuPHOX ligand in a variety of nonpolar solvents, the alkylated products are obtained in up to 99% yield and 99% enantiomeric excess

White-tailed deer (Odocoileus virginianus) population dynamics in a multi-predator landscape

Indices of white-tailed deer (Odocoileus virginianus) abundance in the western Upper Peninsula of Michigan suggested the population declined 40% from the previous 5 year mean following 2 consecutive severe winters in the mid-1990s and has not since increased in population size. I collected estimates and assessed biological and environmental covariates of survival and recruitment of fawns (\u3c 1 year old) and age-specific reproductive and survival rates of adult females (\u3e 1.6 years old) in the southwestern Upper Peninsula of Michigan from 2009–2011. Reproduction did not appear to regulate population growth, as 92 percent of females were pregnant. Annual survival of adult females was 70 percent across years, but poorer annual survival of fawns across years (44 percent) resulted in recruitment being the most influential vital rate to population growth, which increased10 percent from 2009 to 2010, but decreased 13 percent from 2010 to 2011. Variation in population growth emphasized that annual variation in fawn recruitment may have nullified increased growth over time. Most fawn mortalities occurred within 12 weeks of age, emphasizing this period greatly influenced annual survival rates of fawns, and especially population growth. Therefore, I suggest fawns should be considered the priority cohort for deer population management, including mitigation of factors which limit fawn recruitment. Winter severity effects on nutritional condition of adult females primarily influenced survival of adult females and fawns. However, adult female avoidance of interior lowland forests which had greater wolf (Canis lupus) use and commonly aging and over-browsed vegetation ostensibly reduced fawn recruitment through a lack of hiding vegetation and poorer forage. Also, by adult females raising fawns in habitats near roads, the predatory efficacy of coyotes (C. latrans) on adult females and fawns increased. Although predation was the leading cause of deer mortality, bottom-up effects of winter severity on nutritional condition and resource use appeared to be most influential to sustaining a lack of population increase. Hence, I suggest population growth could be improved through habitat management that increases landscape heterogeneity of early successional forests to enhance year-round browse to increase nutritional condition of adult females and hiding cover for fawns

A Frightening Device for Deterring Deer Use of Cattle Feeders

The presence of bovine tuberculosis (TB) in cattle can negatively impact a state’s economy and cattle industry. In Michigan, USA, wild white-tailed deer (Odocoileus virginianus) are a reservoir for reinfecting cattle herds. Although direct TB transmission between deer and cattle is rare, infected deer may contaminate cattle feed. To mitigate this risk, we designed and evaluated a deer-resistant cattle feeder (DRCF) device for deterring deer from feeders. The device delivered negative stimuli to condition deer to avoid cattle feeders. We tested the device by conducting a comparative change experiment at a high-density captive white-tailed deer operation in northeastern lower Michigan using pretreatment and treatment periods and random allocation of DRCF protection to 3 of 6 feeders during the treatment period. We used animal-activated cameras to collect data on deer use of feeders. Deer use was similar at protected and unprotected feeders during the pretreatment period but was lower at protected feeders during the treatment period. Deer-resistant cattle feeders were 100% effective during the first 2 treatment weeks, 94% during the first 5 weeks, but effectiveness then dropped to 61% during the final week. Excluding problems associated with low battery power and infrared sensors, DRCFs were 99% effective at deterring deer. Our results suggest that DRCFs can effectively limit deer use of cattle feed, potentially with minimal impact on feeding behavior of cattle, thus reducing potential transmission of bovine TB through contaminated feed. By employing DRCFs in bovine TB endemic areas, especially at times that deer are food stressed, agencies and producers can practically and economically reduce the potential for bovine TB to be transmitted from deer to cattle

Food Safety Considerations Related to the Consumption and Handling of Game Meat in North America

Emerging foodborne pathogens present a threat to public health. It is now recognized that several foodborne pathogens originate from wildlife as demonstrated by recent global disease outbreaks. Zoonotic spillover events are closely related to the ubiquity of parasitic, bacterial, and viral pathogens present within human and animal populations and their surrounding environment. Foodborne diseases have economic and international trade impacts, incentivizing effective wildlife disease management. In North America, there are no food safety standards for handling and consumption of free-ranging game meat. Game meat consumption continues to rise in North America; however, this growing practice could place recreational hunters and game meat consumers at increased risk of foodborne diseases. Recreational hunters should follow effective game meat food hygiene practices from harvest to storage and consumption. Here, we provide a synthesis review that evaluates the ecological and epidemiological drivers of foodborne disease risk in North American hunter populations that are associated with the harvest and consumption of terrestrial mammal game meat. We anticipate this work could serve as a foundation of preventive measures that mitigate foodborne disease transmission between free-ranging mammalian and human populations

Effects of maternal nutrition, resource use and multi-predator risk on neonatal white-tailed deer survival.

Growth of ungulate populations is typically most sensitive to survival of neonates, which in turn is influenced by maternal nutritional condition and trade-offs in resource selection and avoidance of predators. We assessed whether resource use, multi-predator risk, maternal nutritional effects, hiding cover, or interactions among these variables best explained variation in daily survival of free-ranging neonatal white-tailed deer (Odocoileus virginianus) during their post-partum period (14 May-31 Aug) in Michigan, USA. We used Cox proportional hazards mixed-effects models to assess survival related to covariates of resource use, composite predation risk of 4 mammalian predators, fawn body mass at birth, winter weather, and vegetation growth phenology. Predation, particularly from coyotes (Canis latrans), was the leading cause of mortality; however, an additive model of non-ideal resource use and maternal nutritional effects explained 71% of the variation in survival. This relationship suggested that dams selected areas where fawns had poor resources, while greater predation in these areas led to additive mortalities beyond those related to resource use alone. Also, maternal nutritional effects suggested that severe winters resulted in dams producing smaller fawns, which decreased their likelihood of survival. Fawn resource use appeared to reflect dam avoidance of lowland forests with poor forage and greater use by wolves (C. lupus), their primary predator. While this strategy led to greater fawn mortality, particularly by coyotes, it likely promoted the life-long reproductive success of dams because many reached late-age (>10 years old) and could have produced multiple generations of fawns. Studies often link resource selection and survival of ungulates, but our results suggested that multiple factors can mediate that relationship, including multi-predator risk. We emphasize the importance of identifying interactions among biological and environmental factors when assessing survival of ungulates

Scale Dependence of Female Ungulate Reproductive Success in Relation to Nutritional Condition, Resource Selection and Multi-Predator Avoidance.

Female ungulate reproductive success is dependent on the survival of their young, and affected by maternal resource selection, predator avoidance, and nutritional condition. However, potential hierarchical effects of these factors on reproductive success are largely unknown, especially in multi-predator landscapes. We expanded on previous research of neonatal white-tailed deer (Odocoileus virginianus) daily survival within home ranges to assess if resource use, integrated risk of 4 mammalian predators, maternal nutrition, winter severity, hiding cover, or interactions among these variables best explained landscape scale variation in daily or seasonal survival during the post-partum period. We hypothesized that reproductive success would be limited greater by predation risk at coarser spatiotemporal scales, but habitat use at finer scales. An additive model of daily non-ideal resource use and maternal nutrition explained the most (69%) variation in survival; though 65% of this variation was related to maternal nutrition. Strong support of maternal nutrition across spatiotemporal scales did not fully support our hypothesis, but suggested reproductive success was related to dam behaviors directed at increasing nutritional condition. These behaviors were especially important following severe winters, when dams produced smaller fawns with less probability of survival. To increase nutritional condition and decrease wolf (Canis lupus) predation risk, dams appeared to place fawns in isolated deciduous forest patches near roads. However, this resource selection represented non-ideal resources for fawns, which had greater predation risk that led to additive mortalities beyond those related to resources alone. Although the reproductive strategy of dams resulted in greater predation of fawns from alternative predators, it likely improved the life-long reproductive success of dams, as many were late-aged (>10 years old) and could have produced multiple litters of fawns. Our study emphasizes understanding the scale-dependent hierarchy of factors limiting reproductive success is essential to providing reliable knowledge for ungulate management

White‐tailed deer exploit temporal refuge from multi‐predator and human risks on roads

Abstract Although most prey have multiple predator species, few studies have quantified how prey respond to the temporal niches of multiple predators which pose different levels of danger. For example, intraspecific variation in diel activity allows white‐tailed deer (Odocoileus virginianus) to reduce fawn activity overlap with coyotes (Canis latrans) but finding safe times of day may be more difficult for fawns in a multi‐predator context. We hypothesized that within a multi‐predator system, deer would allocate antipredation behavior optimally based on combined mortality risk from multiple sources, which would vary depending on fawn presence. We measured cause‐specific mortality of 777 adult (>1‐year‐old) and juvenile (1–4‐month‐old) deer and used 300 remote cameras to estimate the activity of deer, humans, and predators including American black bears (Ursus americanus), bobcats (Lynx rufus), coyotes, and wolves (Canis lupus). Predation and vehicle collisions accounted for 5.3 times greater mortality in juveniles (16% mortality from bears, coyotes, bobcats, wolves, and vehicles) compared with adults (3% mortality from coyotes, wolves, and vehicles). Deer nursery groups (i.e., ≥1 fawn present) were more diurnal than adult deer without fawns, causing fawns to have 24–38% less overlap with carnivores and 39% greater overlap with humans. Supporting our hypothesis, deer nursery groups appeared to optimize diel activity to minimize combined mortality risk. Temporal refuge for fawns was likely the result of carnivores avoiding humans, simplifying diel risk of five species into a trade‐off between diurnal humans and nocturnal carnivores. Functional redundancy among multiple predators with shared behaviors may partially explain why white‐tailed deer fawn predation rates are often similar among single‐ and multi‐predator systems

Resource metrics used to assess resource use of white-tailed deer (<i>Odocoileus virginianus</i>) fawns, Upper Peninsula of Michigan, USA, 2009–2011.

<p>Resource metrics used to assess resource use of white-tailed deer (<i>Odocoileus virginianus</i>) fawns, Upper Peninsula of Michigan, USA, 2009–2011.</p