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Abstract. Global projections for ocean conditions in 2100 predict that the North Pacific will experience some of the largest changes. Coastal processes that drive variability in the region can alter these projected changes but are poorly resolved by global coarse-resolution models. We quantify the degree to which local processes modify biogeochemical changes in the eastern boundary California Current System (CCS) using multi-model regionally downscaled climate projections of multiple climate-associated stressors (temperature, O2, pH, saturation state (Ω), and CO2). The downscaled projections predict changes consistent with the directional change from the global projections for the same emissions scenario. However, the magnitude and spatial variability of projected changes are modified in the downscaled projections for carbon variables. Future changes in pCO2 and surface Ω are amplified, while changes in pH and upper 200 m Ω are dampened relative to the projected change in global models. Surface carbon variable changes are highly correlated to changes in dissolved inorganic carbon (DIC), pCO2 changes over the upper 200 m are correlated to total alkalinity (TA), and changes at the bottom are correlated to DIC and nutrient changes. The correlations in these latter two regions suggest that future changes in carbon variables are influenced by nutrient cycling, changes in benthic–pelagic coupling, and TA resolved by the downscaled projections. Within the CCS, differences in global and downscaled climate stressors are spatially variable, and the northern CCS experiences the most intense modification. These projected changes are consistent with the continued reduction in source water oxygen; increase in source water nutrients; and, combined with solubility-driven changes, altered future upwelled source waters in the CCS. The results presented here suggest that projections that resolve coastal processes are necessary for adequate representation of the magnitude of projected change in carbon stressors in the CCS. 

Abstract Structurally complex diazo‐containing scaffolds are formed by conjugate addition to vinyl diazonium salts. The electrophile, a little studied α‐diazonium‐α,β‐unsaturated carbonyl compound, is formed at low temperature under mild conditions by treating β‐hydroxy‐α‐diazo carbonyls with Sc(OTf)₃. Conjugate addition occurs selectively at the 3‐position of indole to give α‐diazo‐β‐indole carbonyls, and enoxy silanes react to give 2‐diazo‐1,4‐dicarbonyl products. These reactions result in the formation of tertiary and quaternary centers, and give products that would be otherwise difficult to form. Importantly, the diazo functional group is retained within the molecule for future manipulation. Treating an α‐diazo ester indole addition product with Rh₂(OAc)₄caused a rearrangement to occur to give a 2‐(1H‐indol‐3‐yl)‐2‐enoate. In the case of diazo ketone compounds, this shift occurred spontaneously on prolonged exposure to the Lewis acidic reaction conditions.