Biomimetic Epxidation of Alkenes by Phenyliodonium Diacetate [PhI(OAc)_2] in the Presence of Mn(Ⅲ) Complex of meso-Tetrakis(4-methoxyphenylporphyrin) Acetate Mn[(T4-OCH_3P)P]OAc

We have reported that phenyliodonium diacetate[PhI（OAc）2] can serve as an eco-friendly mild oxidant for the epoxidation of alkenes in the presence of Mn（III） complex of meso-tetrakis（4-methoxyphenylporphyrin） acetate Mn[（T4-OCH3P）P]OAc and imidazole in CH2Cl2.The amounts of the products（%） and selectivities are very dependent upon the electronic and steric properties of the starting alkenes.To evaluate the validity of this catalytic system for C ＂H activation,cyclohexane and ethylbenzene were oxidized under the epoxidation conditions.

Hydrogenation of Alkenes with NaBH4, CH3CO2H, Pd/C in the Presence of O- and N-Benzyl Functions

NaBH4, CH3CO2H, Pd/C has been described as an effective reagent system to hydrogenate alkenes. Here, we show that the hydrogenation occurs chemoselectively, making it possible to hydrogenate alkenes under Pd/C catalysis with hydrogen created in situ without O- or N-debenzylation.

Tandem Lewis acid catalysis for the conversion of alkenes to 1,2‐diols in the confined space of bifunctional TiSn‐Beta zeolite

The generation of multifunctional isolated active sites in zeolite supports is an attractive method for integrating multistep sequential reactions into a single‐pass tandem catalytic reaction.In this study,bifunctional TiSn‐Beta zeolite was prepared by a simple and scalable post‐synthesis approach,and it was utilized as an efficient heterogeneous catalyst for the tandem conversion of alkenes to 1,2‐diols.The isolated Ti and Sn Lewis acid sites within the TiSn‐Beta zeolite can efficiently integrate alkene epoxidation and epoxide hydration in tandem in a zeolite microreactor to achieve one‐step conversion of alkenes to 1,2‐diols with a high selectivity of>90%.Zeolite confinement effects result in high tandem rates of alkene epoxidation and epoxide hydration as well as high selectivity toward the desired product.Further,the novel method demonstrated herein can be employed to other tandem catalytic reactions for sustainable chemical production.

Application of long-chain alkenones and U_(37)~k values for paleotemperature estimation in the Arctic Chukchi Sea-Bering Sea area

Long-chain alkenones were detected in samples of sea surface sediments from the Chukchi Sea and the Bering Sea areas, the Arctic Pole. The analysis result indicates that C37:3 methylketone is predominate in the long-chain alkenones from the Chukchi and Bering Sea sediments. The abundance of C37 to C39 unsaturated alkenones changes in an order of C37 > C38 > C39. Based on C37 /C38 ratio, the detected organism precursors of the long-chain alkenones are mainly coccolithophrid (Emiliania huxleyi). By the calibration relationship between U37k and U37k indices, the sea surface paleotemperature in these seas is estimated. The estimated values of U37k vary from 4.147℃ to 5.706℃ , with a mean value of 5.092℃.

Functional Polyethylene Glycol with Carboxyl-supported Platinum as an Efficient Catalysis System for the Hydrosilylation of Alkenes

A series of carboxylated long chain polyethylene glycols(abbreviated as PEGCOOH) has been synthesized and used to support chloroplatinic acid.These supported catalysts were then tested for their efficiency in the hydrosilylation of alkenes.The factors affecting their catalytic properties,e.g.relative molecular mass of polyethylene glycol,reaction temperature,platinum content,and type of alkenes,have been studied.It was found that the activity of the platinum catalyst decreased with increasing length of the polyethylene glycol chain,and increased with reaction temperature.Moreover,these catalysts could be reused several times without a noticeable decrease in activity or selectivity.The reaction pathway leading to excellent selectivity for the β-adduct of hydrosilylation of alkenes with triethoxysilane catalyzed by this catalysis system was discussed.

Efficient visible light initiated hydrothiolations of alkenes/alkynes over Ir_(2)S_(3)/ZnIn2S4:Role of Ir_(2)S_(3)

The hydrothiolations of alkynes/alkenes with thiols is an atom-economic and thus attractive method for the constructions of C‒S bonds.Here Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposites with varied Ir_(2)S_(3)loadings were obtained by one-pot solvothermal method from ZnCl_(2),InCl_(3)and thioacetamide with IrCl_(3).The loading of Ir_(2)S_(3)on the surface of ZnIn_(2)S_(4)promoted the hydrothiolations of alkenes and alkynes,with an optimum performance observed over 0.5 mol%Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposite.Based on the studies on the performance of several other cocatalysts(MoS2,NiS and Pd)loaded ZnIn_(2)S_(4)and the EIS analyses,it was proposed that the superior performance over Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposite can be ascribed to an improved efficiency on the photogeneration of the thiyl radicals by loading Ir_(2)S_(3)as well as its inactivity for photocatalytic hydrogen evolution,a side reaction in the light initiated hydrothiolation reaction over ZnIn_(2)S_(4).This study not only demonstrates an efficient and green strategy to synthesize thiolated products under visible light based on semiconductor photocatalysis,but also provides some guidances for the design and development of photocatalytic systems for light induced organic syntheses.

Michael Addition of Amines to Activated Alkenes Promoted by Zn/NH_4Cl System

A Zn/NH4Cl system was exploited at room temperature to promote the Michael addition reaction of various primary and secondary amines with α,β-unsaturated esters,nitriles,amides,and ketones to give the corresponding saturated amines under the mild condition in high yield.

Ultrasonic-enhanced Stereoselective Debromination of vic-Dibromides to Alkenes with Metallic Zinc Powder in Aqueous Media

Carbon-carbon double bond functional groups are often protected through a popular bromination/debromination method because of their reactivity. An ultrasonic-enhanced stereoselective debromination of vic-dibromides with metallic zinc powder in aqueous media has been developed, which generates E-alkenes with excellent yields. The reactivity of vic-dibromides decreases in the order of 1,2-dibromo-1,2-diphenylethane>1,2-dibromo-1-phenylethane>1,2-dibromo-1,2-dialkylethane.

A DFT Study of Alkenes and Alkynes Reacting with H-GaN (0001) Surface

The addition reactions of alkenes and alkynes to the H-terminated GaN （0001） surface with a Ga dangling-bond have been studied employing periodic density functional theory （PDFT） calculations. Detailed information on the reaction pathways of these alkenes and alkynes with H-GaN （0001） surface is provided, which indicates that the reactions contain two steps separated by the metastable intermediates： elementary addition reaction and H-abstraction process. From the energy curves, the reactions are clearly viable in the cases of ethene, styrene and phenylacetylene; while for ethyne, the H-abstraction barrier is higher than the desorption barrier of the intermediate, so the adsorbed C2H2 in intermediate is more likely to be desorbed back into the gas phase than to form a stable adsorbed species. Furthermore, it is obvious that for either alkenes or alkynes, the systems substituted by phenyl have more stable intermediates because π conjugation could improve their stabilities.

Chiral Salen Manganese Complex Immobilized on SBA-15:A New Heterogenized Enantioselective Catalyst forthe Epoxidation of Alkenes

Jacobsen's catalyst was immobilized onto SBA-15 by multi-step grafting, and this heterogenized catalyst exhibited comparable catalytic performance with the corresponding homogeneous counterpart for the epoxidation of alkenes, and the catalyst could be recycled effectively several times.

(Z)-a-Selanyl Alkenyl Grignard Reagents as Convenient Precursors for Stereoselective Synthesis of Trisubstituted Alkenes

Z)-a-Selanyl alkenyl Grignard reagents 2 were prepared conveniently by treatment of a-bromovinylselenides 1 with magnesium filings in THF. Intermediates 2 were reacted with alkyl iodides in the presence of CuI or Pd(PPh3)4 to afford (Z)-1,2-disubstituted vinylselenides 3, which were cross-coupled with Grignard reagents in the presence of (PPh3)2NiCl2 to give trisubstituted alkenes 4 stereoselectively in good yields.

Asymmetric Baylis-Hillman Reaction between Chiral Activated Alkenes and Aromatic Aldehydes in Me_(3)N/H_(2)O/Solvent Medium

Chiral activated alkene, L-menthyl acrylate and （＋）-N-α-phenylethyl acrylamide, induced asymmetric Baylis-HiUman reaction of aromatic aldehydes was realized at 25℃ for 7 days in Me3N/H2O/solvent homogeneous medium. The corresponding Baylis-Hillman adducts were obtained in good chemical yield with moderate to excellent diastereoselectivity （up to 99% de）.

Safe Hydroformylation of Aliphatic Alkene in a Flow Reactor

Despite hydroformylation being a very efficient method for the transformation of alkenes, it is not commonly employed in laboratories owing to the flammable/toxic nature of hydrogen and carbon monoxide gases and the necessity of high-pressure equipment in a batch system. Flow chemistry often raises the safety profiles against high-pressure and toxic gases because the diameter of the flow reactor is small. Herein, we show that aliphatic alkenes can be safely hydroformylated in a flow reactor. In our flow method, although the target hydroformylated product was obtained in a low yield (19%), toxic gases were safely treated using a flow reactor. Better yields could possibly be achieved by recycling of the unreacted alkene.

A New Method for the Transformation of Alkenes intoα, β-Unsaturated Ketones via Cycloaddition with Dichloroketene

A new synthetic method is described here to obtain α, β-unsaturated ketones through alkenes through a sequence involving f (1) cycloaddition of alkenes with dichloroketene, (2) dechlorination of adducts, (3)acidpromoted ring-opening isomerization ofcyclobutanones in CF3 CO2H.

'STEREOSELECTIVE SYNTHESIS OF TRISIJBSTITUTED ALKENES VIA,TITANOCENOCYCLES

By previously reported modified Masai-Rausch method of synthesizing titanocenocycles,followed by acid hydrolysis,trisubstituted al-kenes were synthesized,yields obtained are higher than that reported in literatures.Starting from unsymmetrical alkyne substrates,twelve different types of substituted alkenes were synthesized,among which only two were found single component,others were of mixed isomers.Beside conventional analytical methods,the NMR spectral analysis of titanocenoheterocycle intermediates and the products were used to identify the isomeric structures as well as their relative contents.

A Novel Calix[4]arene Having Long-Chain Monoalkenyl at The Upper Rim

5-1',1'-dimethylundecenyloxyphenylmethyl-11,17,23-tris-1 '',1 ''-dimethylethyl-25,26,27,28-tetrahydroxycalix[4] arene was synthesized from 1,1-dimethylundecenyoxylphenylmethylphenol (3) and bishydroxymethylated p-tert-butylphenol-formaldehyde trimer (7) (3-[3-[3-(Hydroxymethyl)-tert-butylsalicyl-5]-tert-butylsalicy]-5-tert-butyl-2-hydroxybenzyl Alcohol) by '1+3' fragment condensation in dioxane with TiCl4 as condensation agent in 28% yield. It is the first long-chain monoalkenyl substituted calix[4]arene in which the alkenyl was attached to the upper rim of calix[4]arene.

ORGANOPHOSPHINE INITIATED REACTION OF PERFLUOROALKYL IODIDES WITH ALKENES

perfluoroalkyl iodides reacted with alkenes in acetonitrile solu- tion containing catalytic amount of organophosphine under mild condition to give the corresponding adducts in moderate to good yields.Reaction was shown to involve a free radical mechanism.

STUDY ON Cp_2TiCl_2/Fe-INITIATED ADDITION OF 2-HALOTETRAFLUOROETHYL IODIDES TO ALKYNES AND ALKENES

Initiated by CP_2TiCl_2/Fe redox system,2-halotetrafluoroethyl iodides readily reacted with alkynes or alkenes to give 1:1 adducts in good to excellent yields.

INSERTION OF PTC-GENERATED DICHLOROCARBENE INTO C-B BO ND.A FACILE SYNTHESIS OF KETONES FROM ALKENES VIA ORGANOBORATES

The insertion of dichlorocarbene generated from chloroform by Phase Transfer Catalysis(PTC)into carbon-boron bond of dialkylborate anions 3,obtained by method A and B,resulted in the formation of the inter- mediates 5,which were oxidized with alkaline hydrogen peroxide to give the corresponding dialkylketones in 36-77.9% yields.