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A convenient, one-pot, two-component synthesis of 2-(1-amidoalkyl)pyridines is reported, based upon the substitution of suitably-activated pyridine N-oxides by azlactone nucleophiles, followed by decarboxylative azlactone ring-opening. The synthesis obviates the need for precious metal catalysts to achieve a formal enolate arylation reaction, and constitutes a formally ‘umpoled’ approach to this valuable class of bioactive structures.

BackgroundTashiromine (1) is a naturally occurring indolizidine alkaloid. It has been the subject of thirteen successful total syntheses to date. Our own approach centres on the stereoselective construction of the indolizidine core by capture of an electrophilic acyliminium species by a pendant allylsilane. The key cyclisation precursor is constructed using olefin cross-metathesis chemistry, which has the potential to facilitate both racemic and asymmetric approaches, depending upon the choice of the allylsilane metathesis partner.ResultsThe use of the allyltrimethylsilane cross-metathesis approach enables the rapid construction of the key cyclisation precursor 3 (3 steps from commercial materials), which undergoes acid-induced cyclisation to give the desired bicyclic indolizidine skeleton as a 96:4 mixture of diastereomers. Simple functional group interconversions allowed the completion of the total synthesis of racemic tashiromine in six steps (19% overall yield). Three chiral α-alkoxyallylsilanes (12, 14 and 15) were prepared in enantioenriched form and their cross-metathesis reactions studied as part of a putative asymmetric approach to tashiromine. In the event, α-hydroxysilane 12 underwent isomerisation under the reaction conditions to acylsilane 17, while silanes 14 and 15 were unreactive towards metathesis.ConclusionA concise, stereoselective total synthesis of racemic tashiromine has been developed. Attempts to translate this into an asymmetric synthesis have thus far been unsuccessful.

BackgroundAllenylsilanes are useful intermediates in organic synthesis. An attractive, convergent but little used approach for their synthesis is the alkylidenation of stable silylketenes. Reactions thus far have been limited to the use of unsubstituted silylketenes (or equivalents) with stabilised or semi-stabilised ylides only. The current study explores the reactions of substituted ketenes prepared through rhodium(II)-mediated rearrangement of silylated diazoketones.ResultsA range of novel 1,3-disubstituted and 1,3,3-trisubstituted allenylsilanes were prepared using stabilised and semi-stabilised ylides. Alkylidenation with non-stabilised phosphorus ylides was not viable, but the use of titanium-based methylenating reagents was successful, allowing access to 1-substituted allenylsilanes.ConclusionMany novel allenylsilanes may be accessed by alkylidenation of substituted silylketenes. Importantly, for the first time, simple methylenation of silylketenes has been achieved using titanium carbenoid-based reagents.

During the first half of their main-sequence lifetimes, stars rapidly lose angular momentum to their magnetized winds, a process known as magnetic braking. Recent observations suggest a substantial decrease in the magnetic braking efficiency when stars reach a critical value of the Rossby number, the stellar rotation period normalized by the convective overturn timescale. Cooler stars have deeper convection zones with longer overturn times, reaching this critical Rossby number at slower rotation rates. The nature and timing of the transition to weakened magnetic braking have previously been constrained by several solar analogs and two slightly hotter stars. In this Letter, we derive the first direct constraints from stars cooler than the Sun. We present new spectropolarimetry of the old G8 dwarf τ Cet from the Large Binocular Telescope, and we reanalyze a published Zeeman Doppler image of the younger G8 star 61 UMa, yielding the large-scale magnetic field strengths and morphologies. We estimate mass-loss rates using archival X-ray observations and inferences from Ly α measurements, and we adopt other stellar properties from asteroseismology and spectral energy distribution fitting. The resulting calculations of the wind braking torque demonstrate that the rate of angular momentum loss drops by a factor of 300 between the ages of these two stars (1.4–9 Gyr), well above theoretical expectations. We summarize the available data to help constrain the value of the critical Rossby number, and we identify a new signature of the long-period detection edge in recent measurements from the Kepler mission.

The bright star λ Ser hosts a hot Neptune with a minimum mass of 13.6 M _⊕ and a 15.5 day orbit. It also appears to be a solar analog, with a mean rotation period of 25.8 days and surface differential rotation very similar to the Sun. We aim to characterize the fundamental properties of this system and constrain the evolutionary pathway that led to its present configuration. We detect solar-like oscillations in time series photometry from the Transiting Exoplanet Survey Satellite, and we derive precise asteroseismic properties from detailed modeling. We obtain new spectropolarimetric data, and we use them to reconstruct the large-scale magnetic field morphology. We reanalyze the complete time series of chromospheric activity measurements from the Mount Wilson Observatory, and we present new X-ray and ultraviolet observations from the Chandra and Hubble space telescopes. Finally, we use the updated observational constraints to assess the rotational history of the star and estimate the wind braking torque. We conclude that the remaining uncertainty on the stellar age currently prevents an unambiguous interpretation of the properties of λ Ser, and that the rate of angular momentum loss appears to be higher than for other stars with a similar Rossby number. Future asteroseismic observations may help to improve the precision of the stellar age.

We report the discovery of TOI-4562b (TIC-349576261), a Jovian planet orbiting a young F7V-type star, younger than the Praesepe/Hyades clusters (