Avenue to novel o-carboranyl boron compounds - reactivity study of o-carborane-fused aminoborirane towards organic azides.

Herein we report the reactivity study of o-carborane-fused bis(trimethylsilyl)aminoborirane towards three different types of organic azides, i.e., aryl, alkyl, and silyl azides. The reaction with ArN3 (Ar = 2,6-iPr2C6H4, 2,6-C6H3Cl2, 2,4,6-C6H2Br3, C6F5) resulted in the cycloaddition of ArN3 to the borirane BN unit accompanied by silyl migration. Conversely, in the reaction with BnN3, only the BnN3 : borirane 1 : 2 ring expansion product was obtained. Finally, the reaction with Me3SiN3 resulted in a formal nitrene insertion product under thermal conditions. All of the newly obtained o-carborane-fused BN-containing heterocycles were fully characterized, and the mechanism of these substituent-dependent reactions was studied using DFT calculations.

A bottleable super-electron-donor for catalytic borylation of aryl halides.

[(Dpp-bian)B(DMAP)]2 (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene, DMAP = 4-(dimethylamino)pyridine), a bottleable super electron donor (SED), was demonstrated to serve as a SED catalyst in the borylation of aryl iodides, bromides, and the more challenging chlorides. Apart from installing Bpin from B2pin2, the SED-catalyzed borylation protocol is also applicable for installing Bdan from Bpin-Bdan. The radical mechanism has been confirmed by the radical trapping and radical clock experiments.

Persistent and Predominantly Localized Boron Radical from the Reduction of a Three-Dimensional Analogue of NHC-Stabilized Borafluorenium.

In this contribution, we reported the three-dimensional (3D) analogues of N-heterocyclic carbene (NHC)-stabilized 9-borafluorenium and 9-borafluorene radical. The radical was fully characterized by cyclic voltammetry (CV), UV-Vis absorption spectroscopy, electron paramagnetic resonance (EPR) and single-crystal X-ray diffraction analyses. The distinct boron-centered radical character of 9-borafluorene radical was corroborated by DFT calculations and EPR analysis.

Facile Synthesis of Uranium Complexes with a Pendant Borane Lewis Acid and 1,2-Insertion of CO into a U-N Bond.

In this contribution, we illustrate uranium complexes bearing a pendant borate (i.e. 1 and 2) or a pendant borane (i.e. 3 and 4) moiety via reaction of the highly strained uranacycle I with various 3-coordinate boranes. Complexes 3 and 4 represent the first examples of uranium complexes with a pendant borane Lewis acid. Moreover, complex 3 was capable of activation of CO, delivering a new CO activation mode, and an abnormal CO 1,2-insertion pathway into a U-N bond. The importance of the pendant borane moiety was confirmed by the controlled experiments.

Indole-3-Carboxylic Acid From the Endophytic Fungus Lasiodiplodia pseudotheobromae LPS-1 as a Synergist Enhancing the Antagonism of Jasmonic Acid Against Blumeria graminis on Wheat.

The discovery of natural bioactive compounds from endophytes or medicinal plants against plant diseases is an attractive option for reducing the use of chemical fungicides. In this study, three compounds, indole-3-carbaldehyde, indole-3-carboxylic acid (3-ICA), and jasmonic acid (JA), were isolated from the EtOAc extract of the culture filtrate of the endophytic fungus Lasiodiplodia pseudotheobromae LPS-1, which was previously isolated from the medicinal plant, Ilex cornuta. Some experiments were conducted to further determine the antifungal activity of these compounds on wheat powdery mildew. The results showed that JA was much more bioactive than indole-3-carbaldehyde and 3-ICA against Blumeria graminis, and the disease severity caused by B. graminis decreased significantly with the concentration increase of JA treatment. The assay of the interaction of 3-ICA and JA indicated that there was a significant synergistic effect between the two compounds on B. graminis in each of the ratios of 3-ICA to JA (3-ICA:JA) ranging from 1:9 to 9:1. When the compound ratio of 3-ICA to JA was 2:8, the synergistic coefficient was the highest as 22.95. Meanwhile, a histological investigation indicated that, under the treatment of JA at 500 µg/ml or 3-ICA:JA (2:8) at 40 µg/ml, the appressorium development and haustorium formation of B. graminis were significantly inhibited. Taken together, we concluded that JA plays an important role in the infection process of B. graminis and that 3-ICA as a synergist of JA enhances the antagonism against wheat powdery mildew.

Facile access to halogenated cationic BC-centered organoborons isoelectronic with alkenyl halides.

A facile strategy to prepare halogenated cationic BC-centered organoboron analogues of alkenyl halides via the reaction between carbodiphosphoranes (CDPs) and aryl dihaloboranes is reported. Structural comparison of the halogen and alkoxy derivatives, as well as detailed computational studies, corroborates the polarized double dative bonding nature of the central BC double bonds.

Complete Genome Sequence of Bacillus amyloliquefaciens EA19, an Endophytic Bacterium with Biocontrol Potential Isolated from Erigeron annuus.

Bacillus amyloliquefaciens strain EA19 is an endophyte isolated from Erigeron annuus with antifungal activity against Blumeria graminis f. sp. tritici, Magnaporthe oryzae, and Fusarium graminearum. The genome sequence of this strain is 3.96 Mb and contains 3,421 coding sequences, which will facilitate an understanding of the mechanisms of biocontrol.

Isolation of a Uranium(III)-Carbon Multiple Bond Complex.

Low-valent uranium-element multiple bond complexes remain scarce, though there is burgeoning interest regarding to their bonding and reactivity. Herein, isolation of a uranium(III)-carbon double bond complex [(Cp*)2 U(CDP)](BPh4 ) (1) comprising a tridentate carbodiphosphorane (CDP) was reported for the first time. Oxidation of 1 afforded the corresponding U(IV) complex [(Cp*)2 U(CDP)](BPh4 )2 (2). The distance between U and C in 2 is 2.481 Å, indicating the existence of a typical U=C double bond, which is further confirmed by quantum chemical calculations. Bonding analysis suggested that the CDP also serves as both σ- and π-donor in complex 1, though a longer U-C bond (2.666(3) Å) is observed. It implies that 1 is the first isolable mononuclear uranium(III) carbene complex. Moreover, these results suggest that CDPs are promising ligands to establish other low-valent f-block metal-carbon multiple bond complexes.

The complete mitochondrial genome of Scorpiops tibetanus (Scorpionida; Euscorpiidae Laurie).

This study is the first to sequence and analyze the mitochondrial genome of Scorpiops tibetanus . The results showed that the total length of mitochondrial genome of Scorpiops tibetanus was 14,825 bp, including 13 protein-coding genes, 22 tRNAs, 2 rRNAs, and 1 control region. According to the complete mitochondrial genome, the phylogenetic tree was established by the Scorpiops tibetanus and six closely related species. Phylogenetic tree analysis showed that the Scorpiops tibetanus is sister species to Heterometrus longimanus. This study provides theoretical references for further exploring the genetic diversity and phylogeny of scorpion.

Solution-Phase Synthesis of a Base-Free Benzoborirene and a Three-Dimensional Inorganic Analogue.

The base-free benzoborirene 1,2-BR-1,2-C6H4 (7) and its three-dimensional inorganic analogue 1,2-BR-1,2-C2B10H10 (13) have been successfully synthesized by Cp2ZrBr2 and LiCl elimination, respectively. The Cl analogue of the key intermediate for the formation of benzoborirene 7 has been isolated and structurally characterized, thus suggesting the reaction pathway via benzyne Zr complex formation, B-Br/Cbenzyne-Zr σ-bond metathesis, and a Cp2ZrBr2 elimination/ring-closing process. The rationality of the reaction pathway has been confirmed by DFT calculations. In addition, the title compounds shared the same reactivity pattern (i.e., 1,3-silyl migration) toward MeIiPr (8), thus allowing for the synthetic approach to the first carborane-substituted iminoborane 14.

Storage and release of two electrons from an electron-rich carbon-carbon bond: boron mediated reversible coupling of DMAP and 9-azajulolidine.

This manuscript describes the preparation of [{(dpp-bian)BBr}Li(DME)3] (2, dpp-bian = 1,2-bis[(2,6-diisopropylphenyl) imino]acenaphthene) and [{(dpp-bian)BL}+Br-] (5, L = DMAP; 6, L = 9-azajulolidine). The 4,4-coupling of DMAP and 2,2-coupling of 9-azajulolidine can be achieved either by the reaction of 2 with L, or by one-electron reduction of borenium cations 5 and 6. Oxidation of 3 and 4 leads to C-C cleavage and regeneration of 5 and 6. All new compounds have been structurally characterized.

Synthesis of Allenyl-Bdan via the Cu(I)-Catalyzed Borylation of Propargylic Alcohols with the Unsymmetric Diboron Reagent (Bpin-Bdan).

The synthesis of allenyl-Bdan has been realized via the Cu(I)-catalyzed borylation of propargylic alcohols. This methodology offers a facile and efficient pathway toward allenyboronates with diverse functional groups due to the simple access to the substrates. The substrates bearing ester groups are well-tolerated in the synthesis of allenyl-Bdan under the Lewis acidic conditions. The structures of two allenyl-Bdan were further confirmed via single-crystal X-ray diffraction.

Identification and evaluation of resistance to powdery mildew and yellow rust in a wheat mapping population.

Deployment of cultivars with genetic resistance is an effective approach to control the diseases of powdery mildew (PM) and yellow rust (YR). Chinese wheat cultivar XK0106 exhibits high levels of resistance to both diseases, while cultivar E07901 has partial, adult plant resistance (APR). The aim of this study was to map resistance loci derived from the two cultivars and analyze their effects against PM and YR in a range of environments. A doubled haploid population (388 lines) was used to develop a framework map consisting of 117 SSR markers, while a much higher density map using the 90K Illumina iSelect SNP array was produced with a subset of 80 randomly selected lines. Seedling resistance was characterized against a range of PM and YR isolates, while field scores in multiple environments were used to characterize APR. Composite interval mapping (CIM) of seedling PM scores identified two QTLs (QPm.haas-6A and QPm.haas-2A), the former being located at the Pm21 locus. These QTLs were also significant in field scores, as were Qpm.haas-3A and QPm.haas-5A. QYr.haas-1B-1 and QYr.haas-2A were identified in field scores of YR and were located at the Yr24/26 and Yr17 chromosomal regions respectively. A second 1B QTL, QYr.haas-1B-2 was also identified. QPm.haas-2A and QYr.haas-1B-2 are likely to be new QTLs that have not been previously identified. Effects of the QTLs were further investigated in multiple environments through the testing of selected lines predicted to contain various QTL combinations. Significant additive interactions between the PM QTLs highlighted the ability to pyramid these loci to provide higher level of resistance. Interactions between the YR QTLs gave insights into the pathogen populations in the different locations as well as showing genetic interactions between these loci.