Title: Dearomative C2-borylation of indoles
The dearomative functionalization of indoles to C2-borylated indolenium compounds is achieved under mild conditions by leveraging the high Lewis acidity of bis(1-methyl-ortho-carobranyl)borane.  more » « less
Award ID(s):
2349851
PAR ID:
10595380
Author(s) / Creator(s):
; ;
Publisher / Repository:
Royal Society of Chemistry
Date Published:
Journal Name:
Dalton Transactions
Volume:
54
Issue:
14
ISSN:
1477-9226
Page Range / eLocation ID:
5664 to 5667
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Blair, Jaime E (Ed.)
    We examined the evolutionary history ofPhytophthora infestansand its close relatives in the 1c clade. We used whole genome sequence data from 69 isolates ofPhytophthoraspecies in the 1c clade and conducted a range of genomic analyses including nucleotide diversity evaluation, maximum likelihood trees, network assessment, time to most recent common ancestor and migration analysis. We consistently identified distinct and later divergence of the two MexicanPhytophthoraspecies,P.mirabilisandP.ipomoeae, fromP.infestansand other 1c clade species.Phytophthora infestansexhibited more recent divergence from other 1c clade species ofPhytophthorafrom South America,P.andinaandP.betacei. Speciation in the 1c clade and evolution ofP.infestansoccurred in the Andes.P.andina–P.betacei–P.infestansformed a species complex with indistinct species boundaries, hybridizations between the species, and short times to common ancestry. Furthermore, the distinction between modern Mexican and South AmericanP.infestansproved less discrete, suggesting gene flow between populations over time. Admixture analysis indicated a complex relationship among these populations, hinting at potential gene flow across these regions. HistoricP.infestans, collected from 1845–1889, were the first to diverge from all otherP.infestanspopulations. Modern South American populations diverged next followed by Mexican populations which showed later ancestry. Both populations were derived from historicP.infestans. Based on the time of divergence ofP.infestansfrom its closest relatives,P.andinaandP.betaceiin the Andean region, we consider the Andes to be the center of origin ofP.infestans, with modern globalization contributing to admixture betweenP.infestanspopulations today from Mexico, the Andes and Europe. 
    more » « less
  2. Abstract Letk(B0) andl(B0) respectively denote the number of ordinary andp-Brauer irreducible characters in the principal blockB0of a finite groupG. We prove that, ifk(B0)−l(B0) = 1, thenl(B0) ≥p− 1 or elsep= 11 andl(B0) = 9. This follows from a more general result that for every finite groupGin which all non-trivialp-elements are conjugate,l(B0) ≥p− 1 or elsep= 11 and$$G/{{\bf{O}}_{{p^\prime }}}(G) \cong C_{11}^2\, \rtimes\,{\rm{SL}}(2,5)$$ G/ Op′ (G)≅ C112 ⋊SL(2,5) . These results are useful in the study of principal blocks with few characters. We propose that, in every finite groupGof order divisible byp, the number of irreducible Brauer characters in the principalp-block ofGis always at least$$2\sqrt {p - 1} + 1 - {k_p}(G)$$ 2 p−1 +1−kp(G) , wherekp(G) is the number of conjugacy classes ofp-elements ofG. This indeed is a consequence of the celebrated Alperin weight conjecture and known results on bounding the number ofp-regular classes in finite groups. 
    more » « less
  3. Abstract Buffelgrass [Pennisetum ciliare(L.) Link] is an invasive C4perennial bunchgrass that is a threat to biodiversity in aridlands in the Americas and Australia. Topography influencesP. ciliareoccurrence at large spatial scales, but further investigation into the relationship between local-scale topography andP. ciliaregrowth and reproduction would be beneficial. Further, density-dependent effects onP. ciliaregrowth and reproduction have been demonstrated in greenhouse experiments, but the extent to which density dependence influencesP. ciliarein natural populations warrants further investigation. Here we present a study on the relationships between local-scale topography (aspect and slope gradient) and vegetation characteristics (shrub cover,P. ciliarecover, andP. ciliaredensity) and their interactions on individualP. ciliareplant size and reproduction. We measured slope gradient, aspect, shrub cover,P. ciliarecover,P. ciliaredensity, and the total number of live culms and reproductive culms of 10P. ciliareplants in 33 4 by 4 m plots located in 11 transects at the Desert Laboratory at Tumamoc Hill, Tucson, AZ, USA. We modeled the relationships at the local scale of (1)P. ciliarecover and density with aspect and slope gradient and (2)P. ciliaresize and reproduction with abiotic (slope gradient and aspect) and biotic (P. ciliarecover and density and native shrub and cacti cover) characteristics. Aspect and slope gradient were poor predictors ofP. ciliarecover and density in already invaded sites at the scale of our plots. However, aspect had a significant relationship withP. ciliareplant size and reproduction.Pennisetum ciliareplants on south-facing aspects were larger and produced more reproductive culms than plants on other aspects. Further, we found no relationship betweenP. ciliaredensity andP. ciliareplant size and reproduction. Shrub cover was positively correlated withP. ciliarereproduction. South-facing aspects are likely most vulnerable to fast spread and infilling by newP. ciliareintroductions. 
    more » « less
  4. Context.Theγprocess in core-collapse supernovae (CCSNe) can produce a number of neutron-deficient stable isotopes heavier than iron (pnuclei). However, current model predictions do not fully reproduce solar abundances, especially for92, 94Mo and96, 98Ru. Aims.We investigate the impact of different explosion energies and parametrizations on the nucleosynthesis ofpnuclei, by studying stellar models with different initial masses and different CCSN explosions. Methods.We compared thep-nucleus yields obtained using a semi-analytical method to simulate the supernova to those obtained using hydrodynamic models. We explored the effect of varying the explosion parameters on thep-nucleus production in two sets of CCSN models with initial masses of 15, 20, and 25M⊙at solar metallicity. We calculated a new set of 24 CCSN models (eight for each stellar progenitor mass) and compared our results with another recently published set of 80 CCSN models that includes a wide range of explosion parameters: explosion energy or initial shock velocity, energy injection time, and mass location of the injection. Results.We find that the totalp-nucleus yields are only marginally affected by the CCSN explosion prescriptions if theγ-process production is already efficient in the stellar progenitors due to a C−O shell merger. In most CCSN explosions from progenitors without a C−O shell merger, theγ-process yields increase with the explosion energy by up to an order of magnitude, depending on the progenitor structure and the CCSN prescriptions. The general trend of thep-nucleus production with the explosion energy is more complicated if we look at the production of singlepnuclei. The lightp-nuclei tend to be the most enhanced with increasing explosion energy. In particular, for the CCSN models where theα-rich freeze-out component is ejected, the yields of the lightestpnuclei (including92, 94Mo and96Ru) increase by up to three orders of magnitude. Conclusions.We provide the first extensive study using different sets of massive stars of the impact of varying CCSN explosion prescriptions on the production ofpnuclei. Unlike previous expectations and recent results in the literature, we find that the average production ofpnuclei tends to increase with the explosion energy. We also confirm that the pre-explosion production ofpnuclei in C−O shell mergers is a robust result, independent of the subsequent explosive nucleosynthesis. More generally, a realistic range of variations in the evolution of stellar progenitors and in the CCSN explosions might boost the CCSN contribution to the galactic chemical evolution ofpnuclei. 
    more » « less
  5. Abstract Soil biota have strong effects on plants, but we have a poor understanding of how plant chemistry might modify these effects. We examined the effect of soil biota associated with an exotic invasive tree,Prosopis juliflora, versus that associated with native species, from seven sites across India on conspecifics and two other plant species. We then measured changes in species‐specific soil biota effects (identified as plant–soil feedbacks, PSFs) when leaf leachate fromP. julifloraor from native plant species was added to soil containing respective live and sterile soil inoculum.We quantified the amino acid L‐tryptophan from leaf leachate ofP. juliflora,Leucaena leucocephala(another invader), and two native species. We also tested effects ofP. julifloraor native species soil inoculum amendment of tryptophan onP. juliflora,P. cinerariaandL. leucocephalaacross seven sites. We then quantified the microbially metabolized derivatives of tryptophan, phytohormone indole‐3‐acetic acid (IAA) and intermediates after adding tryptophan intoP. julifloraand native soils.Soil biota associated withP. julifloragenerated positive effects on conspecifics andL. leucocephala, but negative effects on the native congenerP. cineraria. WhenP. julifloraleaf leachate was added to soil with liveP. juliflorainoculum, PSFs became more positive forP. julifloraand other species, compared to leaf leachate amended with sterile soil inoculum. Native leaf leachate interacted weakly with soil biota to impact biomass of conspecifics and heterospecifics.There was roughly 10× more tryptophan in the leaf leachate ofP. juliflorathan in the leaf leachate of other species. Tryptophan generally increased positive PSFs associated withP. juliflorarelative to soil biota associated with other plant species. When tryptophan was added to liveP. juliflorasoil, IAA and its intermediates were produced at five of seven sites, and at four of these sites soil biota fromP. juliflorahad positive PSFs.Synthesis. These results provide the first experimental evidence that a chemical leached from the leaves of an invader regulates PSFs. Our results indicate that canopy effects and PSFs, which are usually studied independently, can interact in ways that strongly affect conspecifics and neighbouring species. 
    more » « less