Palladium-Catalyzed Desulfinative Cross-Coupling of Polyhalogenated Aryl Triflates with Aryl Sulfinate Salts:Inversion of Traditional Chemoselectivity

Comprehensive Summary This paper presents the first general examples of palladium-catalyzed desulfinative cross-coupling reaction of polyhalogenated aryl triflates with aryl sulfinate salts showing an inversion of the conventional reactivity order of C-Br>C-Cl>C-OTf.The catalyst system,comprising of Pd(OAc)_(2)and tBuPhSelectPhos,exhibited excellent catalytic reactivity and chemoselectivity toward this reaction.This reaction had a wide range of substrate scopes and provided a simple and efficient method for the construction of functionalized biaryl motifs.Notably,the C-H···Pd interaction from the methine hydrogen of the C2-cyclohexyl group of the indolyl phosphine ligand with the Pd center may contribute a key factor in reactivity and chemoselectivity.Assisting with density functional theory(DFT)calculations,the results revealed that the oxidative addition step in this reaction was a controlling-chemoselectivity step.

Polyhalogenated carbazoles induce hepatic metabolic disorders in mice via alteration in gut microbiota

Polyhalogenated carbazoles(PHCZs)have been widely accepted as emerging pollutants,whereas their ecological and health risks remain uncertain.Herein,female and male Sprague-Dawley(SD)mice were treated with four typical PHCZs to investigate their negative consequences,along with alternations in gutmicrobiota to indicate underlyingmechanisms.In female mice,the relative liver weight ratio increased after four PHCZs exposure;2-bromocarbazole(2-BCZ)increased urine glucose level;3-bromocarbazole(3-BCZ)decreased the glucose and total cholesterol levels;3,6-dichlorocarbazole(3,6-DCCZ)decreased glucose level.The only disturbed biochemical index in male mice was the promoted alkaline phosphatase(ALP)level by 3,6-DCCZ.We also found that the differential blood biochemical indices were correlated with gut microbiota.3-BCZ and 3,6-DCCZ altered Bacteroidetes and Proteobacteria phyla in female and male mice,which were correlated with metabolic disorders.Our findings demonstrated the correlation between PHCZs induced potential hepatotoxicity andmetabolic disordersmay be due to their dioxin-like potentials and endocrine disrupting activities,and the gender differences might result from their estrogenic activities.Overall,data presented here can help to evaluate the ecological and health risks of PHCZs and reveal the underlying mechanisms.

PM_(2.5)-bound polyhalogenated carbazoles(PHCZs)in urban Beijing,China:Occurrence and the source implication

Polyhalogenated carbazoles(PHCZs)are recently raising much attention due to their toxicity and ubiquitous environmental distribution.However,little knowledge is known about their ambient occurrences and the potential source.In this study,we developed an analytical method based on GC-MS/MS to simultaneously determine 11 PHCZs in PM_(2.5) from urban Beijing,China.The optimized method provided low method limit of quantifications(MLOQs,1.45–7.39 fg/m^(3))and satisfied recoveries(73.4%–109.5%).This method was applied to analyze the PHCZs in the outdoor PM_(2.5)(n=46)and fly ash(n=6)collected from 3 kinds of surrounding incinerator plants(steel plant,medical waste incinerator and domestic waste incinerator).The levels of Σ_(11)PHCZs in PM_(2.5) ranged from 0.117 to 5.54 pg/m^(3)(median 1.18 pg/m^(3)).3-chloro-9H-carbazole(3-CCZ),3-bromo-9H-carbazole(3-BCZ),and 3,6-dichloro-9Hcarbazole(36-CCZ)were the dominant compounds,accounting for 93%.3-CCZ and 3-BCZ were significantly higher in winter due to the high PM_(2.5) concentration,while 36-CCZ was higher in spring,which may be related to the resuspending of surface soil.Furthermore,the levels of11PHCZs in fly ash ranged from 338 to 6101 pg/g.3-CCZ,3-BCZ and 36-CCZ accounted for 86.0%.The congener profiles of PHCZs between fly ash and PM_(2.5) were highly similar,indicating that combustion process could be an important source of ambient PHCZs.To the best of our knowledge,this is the first research providing the occurrences of PHCZs in outdoor PM_(2.5).

Study on Differential Rate Kinetics Analysis Based on the Substitution Reaction of Rare Earth-PHA with CyDTA

The kinetic behaviours of the substitution reaction of rare earth-PHA with CyDTA were studied systemati- cally.The relationship between the rate constant and atomic number was discussed.The rate differentiation val- ue R_d(R_d=lgk_(z+n)-lgk_z)was proposed to evaluate the possibility of differential kinetic analysis.The R_d value between the neighbouring lanthanide ions first increases and then decreases along with increasing atomic number, so that the middle and heavy rare earth mixture(such as Sm-Gd and Gd-Y)are ideal systems for the differential rate kinetic analysis.

High Amounts of Halogenated Natural Products in Sperm Whales(Physeter macrocephalus)from Two Italian Regions in the Mediterranean Sea

Halogenated natural products(HNPs)are considered to be emerging contaminants whose environmental distribution and fate are only incompletely known.Therefore,several persistent and bioaccumulative HNP groups,together with manmade polychlorinated biphenyls(PCBs)and polybrominated diphenyl ethers(PBDEs),were quantified in the blubber of nine sperm whales(Physeter macrocephalus)stranded on the coast of the Mediterranean Sea in Italy.The naturally occurring polybrominated hexahydroxanthene derivatives(PBHDs;sum of TetraBHD and TriBHD)were the most prominent substance class with up to 77,000 ng/g blubber.The mean PBHD content(35,800 ng/g blubber)even exceeded the one of PCBs(28,400 ng/g blubber),although the region is known to be highly contaminated with manmade contaminants.Based on mean values,Q1∼PBDEs>MeO-BDEs∼2,2′-diMeO-BB 80 and several other HNPs followed with decreasing amounts.All blubber samples contained an abundant compound whose molecular formula(C_(16)H_(19)Br_(3)O_(2))was verified using high-resolution mass spectrometry.The only plausible matching isomer was(2S,4′S,9R,9′S)-2,7-dibromo-4′-bromomethyl-1,1-dimethyl-2,3,4,4′,9,9′-9,9′-hexahydro-1H-xanthen-9-ol(OH-TriBHD),a hydroxylated secondary metabolite previously detected together with TriBHD and TetraBHD in a sponge known to be a natural producer of PBHDs.The estimated mean amount of the presumed OH-TriBHD was 3000 ng/g blubber,which is unexpectedly high for hydroxylated compounds in the lipids of marine mammals.

Halogen-bond induced unusual polyhalogen anions formation in hydrogen-bonded frameworks to secure iodine sequestration

Safe confinement of fission iodine isotopes for long-term radioactive waste disposal remains a formidable challenge,as conventional sorbents provide inherently weak iodine-host interactions.We report here a novel halogen bond(X-bond)directed strategy to sequester volatile iodine in hydrogen-bonded(H-bonded)frameworks with unprecedented stability.Charge-assisted Hbonded frameworks bearing open halide sites are developed,showing distinctive iodine encapsulation behaviors without compromising the crystallinity.Direct crystallographic evidence indicates the formation of X-bonds,i.e.,I–I···Cl^(−) and I–I···Br^(−),within the confined pore channels.Unusual polyhalogen anions,i.e.,[I_(2)Cl_(2)]^(2−)and[I_(2)Br_(2)]^(2−),sustained in H-bonded frameworks are identified for the first time.The X-bond reinforced host-guest interaction affords robust iodine trapping without leaking out even at elevated temperatures up to 180℃.By integrating the halogen-bond chemistry with H-bonded frameworks,this study offers fresh concepts for developing effective host reservoirs to secure fission iodine isotopes from spent fuel reprocessing off-gases.