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The formation of highly substituted cyclopentenols was developed using a Claisen−Sakurai reaction. Both elements of the reaction can be performed in a one-pot sequence that provides the corresponding cyclized products in high stereoselectivity. The stereochemical outcome is defined by a combination of Claisen stereospecificity and stereoelectronic effects in the Sakurai cyclization that promotes reactivity via an anti-SE′ antiperiplanar transition state. This was determined by examination of the product stereochemistry and through detailed DFT analysis.more » « less
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An auto-tandem catalytic, branched-selective rearrangement of substituted N-alloc-N-allyl ynamides was developed. This reaction provides ready access to complex quaternary nitrile products with vinylogous stereocentres in excellent diastereoselectivity, including contiguous all-carbon quaternary centres. The stereochemical outcome is determined via a Pd(0) catalysed dipolar ketenimine aza-Claisen rearrangement and computational studies exemplify the key role ligand geometry plays.more » « less
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Abstract Axial Seamount is a seafloor volcano with frequent eruptions and periodic cycles of inflation and deflation. Seafloor pressure gauges monitor vertical deformation with time, but inherent instrumental drift complicates and biases geodetic interpretation. A drift corrected pressure recorder was deployed on Axial Seamount on 6 July 2018, at coordinates 45° 57.29′ North latitude, −130° 0.56′ East longitude, depth 1,535 m. This system includes two independent quartz‐resonant pressure gauges, which nearly continuously observe the seafloor pressure. At regular intervals, the gauges are calibrated in situ with a modified deadweight tester at a pressure within 98% of the nominal seafloor pressure. Using the calibration data, the drift of each gauge has been modeled as a simple linear plus decaying exponential function of time. The two estimated linear sensor drift rates are 0.45 ± 0.12 and 0.36 ± 0.08 kPa/year; the modeled sensor drift represents a significant error if uncorrected. The standard deviations of the drift model residuals are of order 0.06 kPa or 6 mm depth equivalent. Once calibrated, the difference between the two seafloor pressure timeseries exhibits a RMS deviation of ±6 mm at the 90% confidence limit and a linear trend less than 1 mm/year. A time series from July 2018 to December 2021 tracks the inflation of Axial Seamount with differing inflation rates over different time intervals.more » « less
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