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In nature and synthetic chemistry, stereoselective [2+1] cyclopropanation is the most prevalent strategy for the synthesis of chiral cyclopropanes, a class of key pharmacophores in pharmaceuticals and bioactive natural products. One of the most extensively studied reactions in the organic chemist’s arsenal, stereoselective [2+1] cyclopropanation, largely relies on the use of stereodefined olefins, which can require elaborate laboratory synthesis or tedious separation to ensure high stereoselectivity. Here we report engineered hemoproteins derived from a bacterial cytochrome P450 that catalyze the synthesis of chiral 1,2,3-polysubstituted cyclopropanes, regardless of the stereopurity of the olefin substrates used. Cytochrome P450BM3 variant P411-INC-5185 exclusively converts (Z)-enol acetates to enantio- and diastereoenriched cyclopropanes and in the model reaction delivers a leftover (E)-enol acetate with 98% stereopurity, using whole Escherichia coli cells. P411-INC-5185 was further engineered with a single mutation to enable the biotransformation of (E)-enol acetates to α-branched ketones with high levels of enantioselectivity while simultaneously catalyzing the cyclopropanation of (Z)-enol acetates with excellent activities and selectivities. We conducted docking studies and molecular dynamics simulations to understand how active-site residues distinguish between the substrate isomers and enable the enzyme to perform these distinct transformations with such high selectivities. Computational studies suggest the observed enantio- and diastereoselectivities are achieved through a stepwise pathway. These biotransformations streamline the synthesis of chiral 1,2,3-polysubstituted cyclopropanes from readily available mixtures of (Z/E)-olefins, adding a new dimension to classical cyclopropanation methods. 

Dam installation on a deep hydrologically open lake provides the experimental framework necessary to study the influence of outlet engineering and changing base levels on limnogeological processes. Here, high-resolution seismic reflection profiles, sediment cores, and historical water level elevation datasets were employed to assess the recent depositional history of Jackson Lake, a dammed glacial lake located adjacent to the Teton fault in western Wyoming (USA). Prograding clinoforms imaged in the shallow stratigraphy indicate a recent lake-wide episode of delta abandonment. Submerged ∼11–12 m below the lake surface, these Gilbert-type paleo-deltas represent extensive submerged coarse-grained deposits along the axial and lateral margins of Jackson Lake that resulted from shoreline transgression following dam construction in the early 20th century. Other paleo-lake margin environments, including delta plain, shoreline, and glacial (drumlins, moraines) landforms were likewise inundated following dam installation, and now form prominent features on the lake floor. In deepwater, a detailed chronology was established using 137 Cs, 210 Pb, and reservoir-corrected 14 C for a sediment core that spans ∼1654–2019 Common Era (CE). Dam emplacement (1908–1916 CE) correlates with a nearly five-fold acceleration in accumulation rates and a depositional shift towards carbonaceous sediments. Interbedded organic-rich black diatomaceous oozes and tan silts track changes in reservoir water level elevation, which oscillated in response to regional climate and downstream water needs between 1908 and 2019 CE. Chemostratigraphic patterns of carbon, phosphorus, and sulfur are consistent with a change in nutrient status and productivity, controlled initially by transgression-driven flooding of supralittoral soils and vegetation, and subsequently with water level changes. A thin gravity flow deposit punctuates the deepwater strata and provides a benchmark for turbidite characterization driven by hydroclimate change. Because the Teton fault is a major seismic hazard, end-member characterization of turbidites is a critical first step for accurate discrimination of mass transport deposits controlled by earthquakes in more ancient Jackson Lake strata. Results from this study illustrate the influence of dam installation on sublacustrine geomorphology and sedimentation, which has implications for lake management and ecosystem services. Further, this study demonstrates that Jackson Lake contains an expanded, untapped sedimentary archive recording environmental changes in the American West.