α-Olefins are the most abundant petrochemical feedstock beyond alkanes, yet their use in commodity chemical manufacture is largely focused on polymerization and hydroformylation. The development of byproduct-free catalytic C-C bond forming reactions that convert olefins to value-added products remains an important objective. Here, we review catalytic intermolecular reductive couplings of unactivated and activated olefin-derived nucleophiles with carbonyl partners. These processes represent an alternative to the longstanding use of stoichiometric organometallic reagents in carbonyl addition.

Iridium catalyzed primary alcohol oxidation triggers reductive C-O bond cleavage of isoprene oxide to form aldehyde-allyliridium pairs that combine to form products of tert-(hydroxy)-prenylation, a motif found in >2000 terpenoid natural products. Curtin-Hammett effects are exploited to enforce high levels of anti-diastereo- and enantioselectivity in the formation of an all-carbon quaternary center. The present redox-triggered carbonyl additions occur in the absence of stoichiometric byproducts, premetallated reagents and discrete alcohol-to-aldehyde redox manipulations.

Heteroaromatic secondary alcohols react with isoprene to form products of hydrohydroxyalkylation in the presence of ruthenium(0) catalysts generated from Ru3(CO)12 and tricyclohexylphosphine, enabling direct conversion of secondary to tertiary alcohols in the absence of premetallated reagents or stoichiometric byproducts. The putative oxaruthenacycle intermediate has been isolated, characterized and reversible metallacycle formation has been demonstrated.

Chiral iridium complexes modified by SEGPHOS catalyze the 2-propanol mediated reductive coupling of branched allylic acetates 1a–1o with formaldehyde to form primary homoallylic alcohols 2a–2o with excellent control of regio- and enantioselectivity. These processes, which rely on enantiotopic π-facial discrimination of σ-allyliridium intermediates, represent the first examples of enantioselective formaldehyde C-C coupling beyond aldol addition.

Nuclear war would produce dire global consequences for humans and our environment. We simulated climate impacts of US‐Russia and India‐Pakistan nuclear wars in an Earth System Model, here, we report on the ocean impacts. Like volcanic eruptions and large forest fires, firestorms from nuclear war would transport light‐blocking aerosols to the stratosphere, resulting in global cooling. The ocean responds over two timescales: a rapid cooling event and a long recovery, indicating a hysteresis response of the ocean to global cooling. Surface cooling drives sea ice expansion, enhanced meridional overturning, and intensified ocean vertical mixing that is expanded, deeper, and longer lasting. Phytoplankton production and community structure are highly modified by perturbations to light, temperature, and nutrients, resulting in initial decimation of production, especially at high latitudes. A new physical and biogeochemical ocean state results, characterized by shallower pycnoclines, thermoclines, and nutriclines, ventilated deep water masses, and thicker Arctic sea ice. Persistent changes in nutrient limitation drive a shift in phytoplankton community structure, resulting in increased diatom populations, which in turn increase iron scavenging and iron limitation, especially at high latitudes. In the largest US‐Russia scenario (150 Tg), ocean recovery is likely on the order of decades at the surface and hundreds of years at depth, while changes to Arctic sea‐ice will likely last thousands of years, effectively a “Nuclear Little Ice Age.” Marine ecosystems would be highly disrupted by both the initial perturbation and in the new ocean state, resulting in long‐term, global impacts to ecosystem services such as fisheries.