Deprotonation of a Seemingly Hydridic Diborane(6) To Build a B−B Bond

Deprotonation of the doubly arylene-bridged diborane(6) derivative 1 H₂ with (Me₃Si)₃CLi or (Me₃Si)₂NK gives the B−B σ-bonded species M[ 1 H] in essentially quantitative yields (THF, room temperature; M=Li, K, arylene=4,4′-di-tert-butyl-2,2′-biphenylylene). With nBuLi as the base, the yield of Li[ 1 H] drops to 20 % and the 1,1-bis(9-borafluorenyl)butane Li[ 2 H] is formed as a side product (30 %). In addition to the 1,1-butanediyl fragment, the two boron atoms of Li[ 2 H] are linked by a μ-H bridge. In the closely related molecule Li[ 3 H], the corresponding μ-H atom can be abstracted with (Me₃Si)₃CLi to afford the B−B-bonded conjugated base Li₂[ 3 ] (THF, 150 °C; 15 %). Li[ 1 H] and Li[ 2 H] were characterized by NMR spectroscopy and X-ray crystallography.     

Taxuchin B,a New Chlorine-Containing Taxoid

ProjectSuppotedbyagrantfromTheNationalNaturalScienceFoundaionofChina.ChemicalstUdiesonTaxusspp.plantShavebeenextensivelycarriedoutsincetheisolationofanticancerdrugpacIitaxel(rtaxol@)fromstembarkofpacificyewTaxusbrevghld').Morethan2ootaxoidshavebeenisolatedfromGenusTaxusandAustrOtaxUSplantS<=).InordertoovercometaxoIsupplycrisis,manyusefulmethodswerederived.AInongthemsemisynthesisofpaclitaxelanditSanalogsfromitSprecursorssuchaslo-deacetyIbaccatinIIIwhichisabundantintherenewableneedles…     

Triple B≡B bond: from a perfect Lewis structure to a dominant π-back-donation. The need for a reference point

Abstract

Coordination of a B₂ fragment by two σ-donor ligands could lead to complexes with a formal triple B≡B bond L→B≡B←L. Formation of L-B σ-bond leads to excess electrons around the B₂ central fragment. A subsequent direct π-charge transfer from B≡B moiety to the ligands L is a necessary condition for incorporation of BB fragment to the conjugated LBBL system. Quantum-chemical calculations (DFT, CCD, and CAS) show that the stabilization of a linear L-BB-L structure is possible but is accompanied by lowering of the B-B bond order. The ammonia-boryne structure H3N→BB←NH₃, which is studied as a model system, shows a perfect triple BB fragment relative to other LBBL adducts. The comparison of the conjugation between the B₂ fragment and two types of σ-donor ligands, with or without π-back-donation, provides an indication of the character of BB multiple bond. Three studied boryne molecules are calculated to have a high barrier for dissociation XXBBXX→XX?+?BBXX, yet a high reactivity of these compounds is indicated by the low-lying excited states of borynes (ΔE_S0-S1<1.5?eV). The largest gap ΔE_S0-S1～2.6?eV is calculated for the room temperature stable bis-NHC-boryne.     

B−B Cleavage and Ring-Expansion of a 1,4,2,3-Diazadiborinine with N-Heterocyclic Carbenes

A 1,4,2,3-diazadiborinine derivative was found to form Lewis adducts with strong two-electron donors such as N-heterocyclic and cyclic (alkyl)(amino)carbenes. Depending on the donor, some of these Lewis pairs are thermally unstable, converting to sole B,N-embedded products upon gentle heating. The products of these reactions, which have been fully characterized by NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction, were identified as B,N-heterocycles with fused 1,5,2,4-diazadiborepine and 1,4,2-diazaborinine rings. Computational modelling of the reaction mechanism provides insight into the formation of these unique structures, suggesting that a series of B−H, C−N, and B−B bond activation steps are responsible for these “intercalation” reactions between the 1,4,2,3-diazadiborinine and NHCs.     

Syntheses and Bioactivity of 4＂-Sulfonate-5-triphenyl silyl Avermectin B1a and Ivermectin B1a Derivatives

Fourteen new derivatives of avermectin B1a, and ivermectin B1a were synthesized from C5-O-triphenyl silylavermectin B1a and ivermectin B1a (yield from 40% to 83%). Their chemical structures were characterized by means of IR. ^1H NMR, ^13C NMR and FAB-MS spectrometries. Some of them show excellent insecticidal activity.     

B−B Bond Nucleophilicity in a Tetraaryl μ-Hydridodiborane(4) Anion

The tetraaryl μ-hydridodiborane(4) anion [ 2 H]⁻ possesses nucleophilic B−B and B−H bonds. Treatment of K[ 2 H] with the electrophilic 9-H-9-borafluorene (HBFlu) furnishes the B₃ cluster K[ 3 ], with a triangular boron core linked through two BHB two-electron, three-center bonds and one electron-precise B−B bond, reminiscent of the prominent [B₃H₈]⁻ anion. Upon heating or prolonged stirring at room temperature, K[ 3 ] rearranges to a slightly more stable isomer K[ 3 a ]. The reaction of M[ 2 H] (M⁺=Li⁺, K⁺) with MeI or Me₃SiCl leads to equimolar amounts of 9-R-9-borafluorene and HBFlu (R=Me or Me₃Si). Thus, [ 2 H]⁻ behaves as a masked [:BFlu]⁻ nucleophile. The HBFlu by-product was used in situ to establish a tandem substitution-hydroboration reaction: a 1:1 mixture of M[ 2 H] and allyl bromide gave the 1,3-propylene-linked ditopic 9-borafluorene 5 as sole product. M[ 2 H] also participates in unprecedented [4+1] cycloadditions with dienes to furnish dialkyl diaryl spiroborates, M[R₂BFlu].     

SPE-HPLC法测定枸杞中阿维菌素B1a残留量

建立了固相萃取前处理净化技术-高效液相色谱(HPLC)法检测枸杞中阿维菌素B1a残留量的方法.样品用乙腈提取,经C18固相萃取柱净化,采用C18柱(250 mm×4.6 mm i.d.,5 μm)分离,以V(甲醇):V(水)=85:15为流动相,在245 nm下进行检测.阿维菌素B1a在0.20～2.00 μg/mL范围呈良好的线性关系(γ=0.9994);该方法检出限(S/N=3)为0.02mg/kg;添加回收率为88.3%～102.5%,相对标准偏差为2.1%～3.8%.     

Hemislin B Glucoside,a New Lignan from Hemistepta Lyrata

From the ethanolic extract of the whole plant of Hemistepta lyrate Bunge., a new lignan, named hemislin B glucoside,has been isolated and identified as α-(trans-3-methoxy-4-O-β-D-glucopyranosylbenzylidene)-β-(3,4-dimethoxybenzyl)-γ-butyrolactone. Its structure has been established on the basis of UV,IR,FABMS,^1H-NMR,^13C-NMR,HMQC and HMBC spectral analysis.     

Circularly polarized luminescence of rhodamine B in a supramolecular chiral medium formed by a vortex flow

Sucked into the vortex: Hydrogels with embedded Rhodamine?B dye showed stir-induced circularly polarized luminescence (CPL; see picture), the sense of which can be controlled by switching the stir direction from clockwise (CW) to counterclockwise (CCW) with slow cooling from the sol to gel states. The chiral alignment of the dye was erased by heating the sample above the gel-sol transition temperature.     

Total synthesis of sparstolonin B via a palladium-catalyzed aldehyde α-arylation

A concise and convergent total synthesis of sparstolonin B was developed. A palladium-catalyzed aldehyde α-arylation was utilized to construct the carbon skeleton of the natural product. A subsequent simple one-pot procedure effected global deprotection and closure of the final two rings via an unusual autoredox mechanism for the conversion of a bis-hydroquinone intermediate to the natural product. The 6 step synthetic sequence was realized in 18% overall yield.     

Convergent total syntheses of callipeltosides a, B, and C

Going for the hat-trick: The synthesis of the entire callipeltoside family of natural products is described. Key to this synthesis was the coupling of the di-ene-yne and pyran fragments by a diastereoselective alkenylzinc addition allowing rapid access to the common aglycon. Attachment of each relevant L-configured sugar resulted in the first total synthesis of callipeltoside B, and the syntheses of callipeltosides?A and C.     

5-阿维菌素B1a酯的合成及生物活性

阿维菌素B_1a(AVB_1a)与羧酸在DMAP/DCC体系中直接酯化,得到10个5-AVB_1a酯衍生物,产率50%～79%;其化学结构由IR,¹H NMR,¹³CNMR和MS谱确证.生物活性测定结果表明,部分5-阿维菌素B_1a酯衍生物具有良好的杀虫、杀螨活性.     

The B–H–B bridging interaction in B-substituted oxazaborolidine–borane complexes: a theoretical study

Ten oxazaborolidine–borane complexes, nine among them boron-substituted (B–R, R=CH₃, CF₃, and OCH₃), are carefully analysed using quantum-chemistry methods to determine their equilibrium geometries and the corresponding oxazaborolidine–borane interaction energies. It is observed that in all B-trifluoromethyl substituted oxazaborolidine–borane complexes and in one B-methyl substituted complex the B–H–B bond is formed and the interaction energies are 1.5–2.5 times as large as in other investigated complexes. We believe that the presented results may be helpful in experimental recognition of oxazaborolidine–borane complexes which may appear, inter alia, as reaction intermediates.     

Electrodeposition of composite Ni–B coatings in a stirred heterogeneous system

The formation of composite electrochemical coatings of a nickel matrix with boron microparticles was investigated. Electrolytical nickel–boron layers were deposited on a paraffin-impregnated graphite electrode in a stirred heterogeneous system formed by a Watts-type nickel plating bath and dispersed boron powder particles. The polarisation behaviour of the composite plating bath as a function of the boron particle loading was examined. The effect of deposition conditions, as well as of the amount of boron powder in the plating bath on the boron content in the composite Ni–B coatings, was examined. The composite coating structure was established using scanning electron microscopy and light optical microscopy. The distribution of boron particles in the composite deposits was investigated by dynamic secondary ion mass spectrometry. The boron particles content was determined gravimetrically. The obtained results suggest that the content of incorporated boron particles increases with an increasing amount of boron in the plating bath. The potentiodynamic deposition method is demonstrated to be more suitable for production of composite coatings with a high content of boron particles than the potentiostatic one. Homogeneous distribution of boron particles in the nickel matrix without coagulation or sedimentation was associated with the electrochemical fabrication method in stirred heterogeneous systems.     

Synthesis of 4＂-benzyloxyimino-4＂-deoxyavermectin B 1 a derivatives

Six new 4＂-benzyloxyimino-4＂-deoxyavermectin B la derivatives were synthesized from avermectin Bla by the selective protection of C-5-hydroxy group, oxidation of C-4＂-hydroxy group, and deprotection followed by reaction with O-substituted hydroxylamine hydrochlorides. Their structures were confirmed by IR, 1H NMR, 13C NMR and MS. Insecticidal activities of the derivatives against Phopalosiphum pseudobrassicae, Spodoptera exigua and Pluteua xylosteua were evaluated.     

Synthesis of gibbilimbols B and D by a modified Ramberg-Bcklund reaction

Gibbilimbols B and D were synthesized from the facile rearrangement of sulfone in the presence of dibromodifluoromethane and alumina-supported KOH in dichloromethane,followed by refluxing the rearrangement products in conc.HCl and methanol and then treating with thiophenol in the presence of AIBN.     

B[a]A甲基衍生物致癌活性的从头计算研究

甲基多环芳烃的代谢过程中,角环湾区的阳离子及亚甲基阳离子孰是＂终致癌剂＂的理论一直存在争论。本文以B[a]A为例,依据生物体内的代谢模型、应用量子化学从头计算方法和密度泛函理论（DFT）,系统计算了苯并[a]蒽母体及其各个位置取代甲基衍生物代谢过程产物的总能量,发现碳正离子形成的难易程度是引起其致突和致癌活性差异的一个重要因素。计算结果表明,湾区阳离子与甲基阳离子两个亲电活性中心两种作用机制相比较,显然后者的相关性更为明显。