N-Triflylphosphorimidoyl Trichloride: A Versatile Reagent for the Synthesis of Strong Chiral Brønsted Acids

A series of strong Brønsted acids has been synthesized in high yields using N-triflylphosphorimidoyl trichloride as reagent. The syntheses proceed efficiently with electron-rich, electron-deficient, and sterically hindered substrates

Building the Terrestrial Planets: Constrained Accretion in the Inner Solar System

To date, no accretion model has succeeded in reproducing all observed constraints in the inner Solar System. These constraints include 1) the orbits, in particular the small eccentricities, and 2) the masses of the terrestrial planets -- Mars' relatively small mass in particular has not been adequately reproduced in previous simulations; 3) the formation timescales of Earth and Mars, as interpreted from Hf/W isotopes; 4) the bulk structure of the asteroid belt, in particular the lack of an imprint of planetary embryo-sized objects; and 5) Earth's relatively large water content, assuming that it was delivered in the form of water-rich primitive asteroidal material. Here we present results of 40 high-resolution (N=1000-2000) dynamical simulations of late-stage planetary accretion with the goal of reproducing these constraints, although neglecting the planet Mercury. We assume that Jupiter and Saturn are fully-formed at the start of each simulation, and test orbital configurations that are both consistent with and contrary to the "Nice model." We find that a configuration with Jupiter and Saturn on circular orbits forms low-eccentricity terrestrial planets and a water-rich Earth on the correct timescale, but Mars' mass is too large by a factor of 5-10 and embryos are often stranded in the asteroid belt. A configuration with Jupiter and Saturn in their current locations but with slightly higher initial eccentricities (e = 0.07-0.1) produces a small Mars, an embryo-free asteroid belt, and a reasonable Earth analog but rarely allows water delivery to Earth. None of the configurations we tested reproduced all the observed constraints. (abridged)Comment: Accepted to Icarus. 21 pages, 12 figures, 5 tables in emulateapj format. Figures 3 and 4 degraded. For full-resolution see http://casa.colorado.edu/~raymonsn/ms_emulateapj.pd

Asymmetric Catalysis via Cyclic, Aliphatic Oxocarbenium Ions

A direct enantioselective synthesis of substituted oxygen heterocycles from lactol acetates and enolsilanes has been realized using a highly reactive and confined imidodiphosphorimidate (IDPi) catalyst. Various chiral oxygen heterocycles, including tetrahydrofurans, tetrahydropyrans, oxepanes, chromans, and dihydrobenzofurans, were obtained in excellent enantioselectivities by reacting the corresponding lactol acetates with diverse enol silanes. Mechanistic studies suggest the reaction to proceed via a nonstabilized, aliphatic, cyclic oxocarbenium ion intermediate paired with the confined chiral counteranion

An Oort cloud origin for the high-inclination, high-perihelion Centaurs

We analyse the origin of three Centaurs with perihelia in the range 15 AU to 30 AU, inclinations above 70 deg and semi-major axes shorter than 100 AU. Based on long-term numerical simulations we conclude that these objects most likely originate from the Oort cloud rather than the Kuiper Belt or Scattered Disc. We estimate that there are currently between 1 and 200 of these high-inclination, high-perihelion Centaurs with absolute magnitude H<8.Comment: Accepted for publication in MNRA

The Catalytic Asymmetric Mukaiyama–Michael Reaction of Silyl Ketene Acetals with α,β-Unsaturated Methyl Esters

α,β-Unsaturated esters are readily available but challenging substrates to activate in asymmetric catalysis. We now describe an efficient, general, and highly enantioselective Mukaiyama–Michael reaction of silyl ketene acetals with α,β-unsaturated methyl esters that is catalyzed by a silylium imidodiphosphorimidate (IDPi) Lewis acid

Rossiter-McLaughlin Observations of 55 Cnc e

We present Rossiter-McLaughlin observations of the transiting super-Earth 55 Cnc e collected during six transit events between January 2012 and November 2013 with HARPS and HARPS-N. We detect no radial-velocity signal above 35 cm/s (3-sigma) and confine the stellar v sin i to 0.2 +/- 0.5 km/s. The star appears to be a very slow rotator, producing a very low amplitude Rossiter-McLaughlin effect. Given such a low amplitude, the Rossiter-McLaughlin effect of 55 Cnc e is undetected in our data, and any spin-orbit angle of the system remains possible. We also performed Doppler tomography and reach a similar conclusion. Our results offer a glimpse of the capacity of future instrumentation to study low amplitude Rossiter-McLaughlin effects produced by super-Earths.Comment: Accepted for publication in ApJ Letter

Stellar SEDs from 0.3-2.5 Microns: Tracing the Stellar Locus and Searching for Color Outliers in SDSS and 2MASS

The Sloan Digital Sky Survey (SDSS) and Two Micron All Sky Survey (2MASS) are rich resources for studying stellar astrophysics and the structure and formation history of the Galaxy. As new surveys and instruments adopt similar filter sets, it is increasingly important to understand the properties of the ugrizJHKs stellar locus, both to inform studies of `normal' main sequence stars as well as for robust searches for point sources with unusual colors. Using a sample of ~600,000 point sources detected by SDSS and 2MASS, we tabulate the position and width of the ugrizJHKs stellar locus as a function of g-i color, and provide accurate polynomial fits. We map the Morgan-Keenan spectral type sequence to the median stellar locus by using synthetic photometry of spectral standards and by analyzing 3000 SDSS stellar spectra with a custom spectral typing pipeline. We develop an algorithm to calculate a point source's minimum separation from the stellar locus in a seven-dimensional color space, and use it to robustly identify objects with unusual colors, as well as spurious SDSS/2MASS matches. Analysis of a final catalog of 2117 color outliers identifies 370 white-dwarf/M dwarf (WDMD) pairs, 93 QSOs, and 90 M giant/carbon star candidates, and demonstrates that WDMD pairs and QSOs can be distinguished on the basis of their J-Ks and r-z colors. We also identify a group of objects with correlated offsets in the u-g vs. g-r and g-r vs. r-i color-color spaces, but subsequent follow-up is required to reveal the nature of these objects. Future applications of this algorithm to a matched SDSS-UKIDSS catalog may well identify additional classes of objects with unusual colors by probing new areas of color-magnitude space.Comment: 23 pages in emulateapj format, 17 figures, 7 tables. Accepted for publication in the Astronomical Journal. To access a high-resolution version of this paper, as well as machine readable tables and an archive of 'The Hammer' spectral typing suite, see http://www.cfa.harvard.edu/~kcovey v2 -- fixed typos in Table 7 (mainly affecting lines for M8-M10 III stars

MagAO Imaging of Long-period Objects (MILO). I. A Benchmark M Dwarf Companion Exciting a Massive Planet around the Sun-like Star HD 7449

We present high-contrast Magellan adaptive optics (MagAO) images of HD 7449, a Sun-like star with one planet and a long-term radial velocity (RV) trend. We unambiguously detect the source of the long-term trend from 0.6-2.15 \microns ~at a separation of \about 0\fasec 54. We use the object's colors and spectral energy distribution to show that it is most likely an M4-M5 dwarf (mass \about 0.1-0.2 \msun) at the same distance as the primary and is therefore likely bound. We also present new RVs measured with the Magellan/MIKE and PFS spectrometers and compile these with archival data from CORALIE and HARPS. We use a new Markov chain Monte Carlo procedure to constrain both the mass ($> 0.17$ \msun ~at 99$\%$ confidence) and semimajor axis (\about 18 AU) of the M dwarf companion (HD 7449B). We also refine the parameters of the known massive planet (HD 7449Ab), finding that its minimum mass is $1.09^{+0.52}_{-0.19}$ \mj, its semimajor axis is $2.33^{+0.01}_{-0.02}$ AU, and its eccentricity is $0.8^{+0.08}_{-0.06}$. We use N-body simulations to constrain the eccentricity of HD 7449B to $\lesssim$ 0.5. The M dwarf may be inducing Kozai oscillations on the planet, explaining its high eccentricity. If this is the case and its orbit was initially circular, the mass of the planet would need to be $\lesssim$ 1.5 \mj. This demonstrates that strong constraints on known planets can be made using direct observations of otherwise undetectable long-period companions.Comment: Corrected planet mass error (7.8 Mj --> 1.09 Mj, in agreement with previous studies

Thermodynamic perspective on the field-induced behavior of α\alpha-RuCl3_3

Measurements of the magnetic Gr\"uneisen parameter ($\Gamma_B$) and specific heat on the Kitaev material candidate $\alpha$-RuCl$_3$ are used to access in-plane field- and temperature-dependence of the entropy up to 12 T and down to 1 K. No signatures corresponding to phase transitions are detected beyond the boundary of the magnetically ordered region, but only a shoulder-like anomaly in $\Gamma_B$, involving an entropy increment as small as $10^{-5} R\log 2$. These observations put into question the presence of a thermodynamic phase transition between the purported quantum spin liquid and the field-polarized state of $\alpha$-RuCl$_3$. We show theoretically that at low temperatures $\Gamma_B$ is sensitive to crossings in the lowest excitations within gapped phases, and identify the measured shoulder-like anomaly as being of such origin. Exact diagonalization calculations demonstrate that the shoulder-like anomaly can be reproduced in extended Kitaev models that gain proximity to an additional phase at finite field without entering it. We discuss manifestations of this proximity in other measurements.Comment: published version (incl. Supplemental Material