Selective 1,2-Hydroarylation(Alkenylation) of gem-Difluoroalkenes to Access (-CF2 H) Motifs.

An emerging class of C-C coupling transformations that furnish drug-like building blocks involves catalytic hydrocarbonation of alkenes. However, despite notable advances in the field, hydrocarbon addition to gem-difluoroalkenes without additional electronic activation remains largely unsuccessful. This owes partly to poor reactivity and the propensity of difluoroalkenes to undergo defluorinative side reactions. Here, we report a nickel catalytic system that promotes efficient 1,2-selective hydroarylation and hydroalkenylation, suppressing defluorination and providing straightforward access to a diverse assortment of prized organofluorides bearing difluoromethyl-substituted carbon centers. In contrast to radical-based pathways and reactions triggered by hydrometallation via a nickel-hydride complex, our experimental and computational studies support a mechanism in which a catalytically active nickel-bromide species promotes selective carbonickelation with difluoroalkenes followed by alkoxide exchange and hydride transfer, effectively overcoming the difluoroalkene's intrinsic electronic bias.

Rising Sea Levels: Helping Decision-Makers Confront the Inevitable.

Sea-level rise (SLR) is not just a future trend; it is occurring now in most coastal regions across the globe. It thus impacts not only long-range planning in coastal environments, but also emergency preparedness. Its inevitability and irreversibility on long time scales, in addition to its spatial non-uniformity, uncertain magnitude and timing, and capacity to drive non-stationarity in coastal flooding on planning and engineering timescales, create unique challenges for coastal risk-management decision processes. This review assesses past United States federal efforts to synthesize evolving SLR science in support of coastal risk management. In particular, it outlines the: (1) evolution in global SLR scenarios to those using a risk-based perspective that also considers low-probability but high-consequence outcomes, (2) regionalization of the global scenarios, and (3) use of probabilistic approaches. It also describes efforts to further contextualize regional scenarios by combining local mean sea-level changes with extreme water level projections. Finally, it offers perspectives on key issues relevant to the future uptake, interpretation, and application of sea-level change scenarios in decision-making. These perspectives have utility for efforts to craft standards and guidance for preparedness and resilience measures to reduce the risk of coastal flooding and other impacts related to SLR.

Innovations in science and scenarios for assessment.

Scenarios for the Third National Climate Assessment (NCA3) were produced for physical climate and sea level rise with substantial input from disciplinary and regional experts. These scenarios underwent extensive review and were published as NOAA Technical Reports. For land use/cover and socioeconomic conditions, scenarios already developed by other agencies were specified for use in the NCA3. Efforts to enhance participatory scenario planning as an assessment activity were pursued, but with limited success. Issues and challenges included the timing of availability of scenarios, the need for guidance in use of scenarios, the need for approaches to nest information within multiple scales and sectors, engagement and collaboration of end users in scenario development, and development of integrated scenarios. Future assessments would benefit from an earlier start to scenarios development, the provision of training in addition to guidance documents, new and flexible approaches for nesting information, ongoing engagement and advice from both scientific and end user communities, and the development of consistent and integrated scenarios.