POLYMERIZATION MECHANISM OF DIENES WITH HOMOGENEOUS RARE EARTH CATALYSTS

The reaction mechanisms of diene polymerization with homogeneous rare earth catalyst are studied by means of the spectra of ~1H-NMR, one-and two-dimensions ^(13)C-NMR. Based on the data of above NMR spectra, it is proposed that the polymerization reaction proceeds according to the following mechanism: η~4-diene (cis-trans-)and η~3-allyl (syn-anti-).

Electromechanical Properties of Ethylene Propylene Diene Elastomers: Effect of Ethylene Norbornene Content

Ethylene propylene diene elastomers (EPDM) of various side chains and molecular weights were prepared as thin discs and the effects of electric field strength and temperature on the electromechanical properties were investigated. The electrical conductivity, the dielectric constant, the storage and loss moduli (G' and G'), the storage modulus response (ΔG’1000 V/mm), and the storage modulus sensitivity (ΔG’1000 V/mm/G’0) of the elastomers of different ethylene norbornene (ENB) contents and molecular weights were measured under electric field strengths varying from 0 V/mm to 1000 V/mm and at temperatures between 300 K and 380 K. The storage modulus response and sensitivity increase with increasing molecular weight and dielectric constant, consistent with the existing theory. However, for the case of EPDMs with different ENB contents, the storage modulus response and sensitivity vary inversely with the dielectric constant. EDPM is potentially a new type of electroactive materials.

NATURAL PRODUCTS SYNTHESIS BY RETRO-DIELS-ALDER REACTION Ⅱ~1 ASYMMETRIC SYNTHESIS OF (+) AND (-) 5-OXO-ENDO-TRICYCLO [5.2.1.0.^(2, 6)] DECA-3, 8-DIENE 1 BY ENZYME-CATALYZED REACTION

Asymmetric syntheses of both enantiomerically pure (+) and (-) 5-oxo-endo-tricyclo [5.2.1.0.^(2,6)] deca-3, 8-diene 1 was described. The key step is the use of enzyme-catalyzed hydrolysis of meso-diacetate 5.

The Addition Reaction of p-Chlorobenzaldoxime Dehydrodimer with 1,3-Dienes

The addition reaction of p chlorobenzaldoxime dehydrodimer and 1,3 dienes in refluxing chloroform gives linear 1,4 addition products. The reaction is probably a free radical process.

Recent advances in radical‐mediated transformations of 1,3‐dienes

1,3‐Dienes are a class of easily accessible and versatile feedstock chemicals that can participate in a wide range of reactions to facilitate the synthesis of various valuable allylic compounds.In the past decades,radical methodology has emerged as a powerful tool for organic synthesis by virtue of the fact that diverse highly reactive radical species can usually be generated under mild,neutral and controlled conditions,and allow for rapid generation of molecular complexity.In this review,we critically illustrate the recent advances in the field of radical‐mediated transformations of 1,3‐dienes based on the different radical precursors and working modes.Wherever possible,particular emphasis is also put on the related mechanistic studies and synthetic applications.

Crossed Molecular Beams and Theoretical Studies of the O(~3P)+1,2-Butadiene Reaction:Dominant Formation of Propene+CO and Ethylidene+Ketene Molecular Channels

Detailed understanding of the mechanism of the combustion relevant multichannel reactions of O(3P) with unsaturated hydrocarbons (UHs) requires the identification of all primary reaction products, the determination of their branching ratios and assessment of intersystem crossing (ISC) between triplet and singlet potential energy surfaces (PESs). This can be best achieved combining crossed-molecular-beam (CMB) experiments with universal, soft ionization, mass-spectrometric detection and time-of-flight analysis to high-level ab initio electronic structure calculations of triplet/singlet PESs and RRKM/Master Equation computations of branching ratios (BRs) including ISC. This approach has been recently demonstrated to be successful for O(3P) reactions with the simplest UHs (alkynes, alkenes, dienes) containing two or three carbon atoms. Here, we extend the combined CMB/theoretical approach to the next member in the diene series containing four C atoms, namely 1,2-butadiene (methylallene) to explore how product distributions, branching ratios and ISC vary with increasing molecular complexity going from O(3P))+propadiene to O(3P)+1,2-butadiene. In particular, we focus on the most important, dominant molecular channels, those forming propene+CO (with branching ratio ∽0.5) and ethylidene+ketene (with branching ratio ∽0.15), that lead to chain termination, to be contrasted to radical forming channels (branching ratio ∽0.35) which lead to chain propagation in combustion systems.

STUDIES ON POLYMERIZATION MECHANISM OF CONJUGATED DIENE WITH η~3-ALLYL RARE EARTH MODEL COMPLEX

(η^-C_H_5)_2CeCl_5Mg_2(tmed)_2 was used as a catalyst to polymerize isoprene,Terminal ends of polyisoprene were identified as -CH_2-CH=CH_,which indicates that the insertion reaction of the monomer occurred between η^-allyl and cerium ion and gives a direct evidence for the η^-allyl mechanism of conjugated diene polymerzation with rare earth coordination catalysts.

EFFECT OF ELECTRON DONORS ON THE SELECTIVE HYDROGENATION OF DIENE TO MONOENE OVER HETEROGENIZED Pd CATALYST

In the selective hydrogenation of diene (or alkyne) using heterogenized homogeneous catalyst, the high selectivity of monoene formation only appears in a very short time interval. The addition of suitable electron donors can decrease or even cease the monoene hydrogenation and thereby keep the high monoene selectivity after reaching its maximum.

NEW METHODS FOR AROMATIZATION OF STEROIDAL 2,5(10)-DIENES

New methods for dehydrogenation of steroidal 2,5(10)-dienes with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or pyridinium hydrobromide perbromide(PHP,Py·HBr·Br_2) to aromatic A ring steroid in quantitative yield in short time are described.

Studies on the Total Synthesis of Hainanolide(Ⅲ)-Unusual Diene Isomerization in a Diels-Alder Reaction

An unexpected diene isomerization of the triene acid 3 in the Lewis acid catalyzed intramolecular Diels-Alder reaction was observed

One-Pot Production of Substituted Anthraquinones via the Diene Synthesis in the Presence of Mo-V-P Heteropoly Acid Solutions

Acid-catalytic 1,3-butadiene condensation with para-quinones followed by the obtained product oxidation may be performed in one stage as one-pot process, if assisted by the aqueous solutions of Mo-V-P heteropoly acids with a composition of HaPzMoyVxOb. 1,4-naphthoquinone (NQ) condensation with 1,3-butadiene in HPA solutions (brutto-composition H15P4Mo18V7O89 and H17P3Mo16V10O89) in the presence of hydrophylic organic solvents (acetone, 1,4-dioxane) provides 70% yield of 9,10-anthraquinone (AQ) containing no less than 90% AQ. In the same conditions reaction NQ with substituted 1,3-butadienes in the presence of the aqueous H17P3Mo16V10O89 (HPA-10) solution allows to prepare substituted AQ with yield up to 90% and purity up to 99%. The catalysts are regenerated by oxygen in separate stage and are reused.

Pd-Catalyzed Dienylation of Propargylic Esters Enabling Highly Stereoselective Synthesis of Danishefsky-Type Trisubstituted Dienes

The stereochemical synthesis of highly substituted Danishefsky-type dienes remains unsolved in organic chemistry.We describe a simple and efficient approach for the stereoselective synthesis of Danishefsky-type trisubstituted dienes from readily available propargylic esters via Pd-catalyzed dienylation reaction through the key intermediate metallacyclobutene in a regio-,chemo-and stereoselective fashion.This method facilitates a broad range of challenging trisubstituted dienes with a high level of stereocontrol.

Construction of remote cyano-substituted quaternary carbon centers via nickel-catalyzed migratory hydrocyanation of unconjugated dienes

The transition-metal-catalyzed migratory functionalization has emerged as a robust protocol for the building of C–C bonds remote from the“initiation”position.However,a similar strategy for the construction of quaternary carbon centers is still underdeveloped and only a limited number of reports exist.Herein,we report a nickel-catalyzed migratory hydrocyanation of unconjugated dienes to construct remote cyano-substituted quaternary carbon centers.This transformation features exceptional regioselectivity,mild reaction conditions,broad substrate scope and high yields.The synthetic utility of this method has been highlighted by a series of product derivatizations,and the potential of this transformation has been extended to synthesize TRPV1 antagonist and the key intermediate in the total synthesis of quebrachamine.Density functional theory(DFT)studies unveiled that the specific catalytic pocket assumed a significant role in the selective formation of cyano-substituted quaternary carbon centers.

Nickel-Catalyzed Regioselective Hydrosilylation of Conjugated Dienes

With the increasing demand for homoallylic silanes and allylic silanes,the highly efficient and regioselective hydrosilylations of conjugated dienes are urgently needed.Herein,we developed a Ni-catalyzed regiodivergent hydrosilylation of aromatic conjugated dienes by adjusting the temperature and ligands.Under low temperature(-30℃),an eternal-ligand-free system(Ni/t-BuOk)can efficiently facilitate the 3,4-anti-Markovnikov hydrosilylation to provide homoallylic silanes via electrophilic activation process;under room temperature(25℃),a ligand-controlled system(Ni/t-BuOk/PPh3)can eventuate the 3,4-Markovnikov hydrosilylation to produce allylic silanes via Chalk-Harrod process.Both systems are compatible with various conjugated dienes and primary silanes in excellent yields andregioselectivities.

Enantioselective and stereodivergent hydromonofluoroalkylation of conjugated and remote diene

Because of the widespread applications of optically active alkyl fluorides in medicinal and agro chem-icals,enantioselective and even stereodivergent construction of alkyl fluorides remains highly desirable but underdeveloped.Transition-metal-catalyzed asymmetric hydrofluoroalkylation of readily available di-enes represents a novel route to achieve this goal,yet receives scarce study.Here we report an intrigu-ing palladium-catalyzed enantioselective hydromonofluoroalkylation reaction of conjugated dienes.Both monosubstituted and internal dienes proceed well with the transformation and furnish alkyl fluorides in generally>80%yield and>90%ee.A stereodivergent hydromonofluoroalkylation protocol via Pd/Cu co-catalysis is also established for the access to all four stereoisomers of corresponding moieties bear-ing a fully-substituted F-stereogenic center and vicinal tertiary carbon center.In addition,asymmetric migratory hydromonofluoroalkylation of skipped dienes is developed to realize the direct allylic C-H flu-oroalkylation.A compound library of enantioenriched cyclic fluorides is thus built to highlight the trans-formation potential of present methodology.

Self-healing Behavior of Ethylene Propylene Diene Rubbers Based on Ionic Association

To meet the increasing demand for safe, environmentally friendly and high-performance smart materials, self-healing rubbers are highly desired. Here, the self-healing performance of ethylene propylene diene monomer rubber (EPDM) is reported, which was designed by graft-polymerization of zinc dimethacrylate (ZDMA) onto rubber chains to form a reversible ionic cross-linked network. Single ionic cross-linked network and dual network, combining covalent and ionic cross-links, could be tuned by controlling vulcanization process to achieve tailorable mechanical and self-healing properties. It was found that ionic cross-linked EPDM showed a recovery of more than 95% of the original mechanical strength through a healing process of 1 h at 100 °C. The covalent cross-links could improve mechanical properties but block self-healing. Adding 50 wt% liquid rubber to “dry” EPDM could effectively enhance self-healing capability of the dual cross-linked network and the healed tensile strength could reach 0.9 MPa. A compromise between mechanical performance and healing capability could be potentially tailored by controlling vulcanization process and liquid rubber content.

Chiral Dienes: From Ligands to FLP Catalysts

Olefins are very easily accessible compounds which are both popular substrates in synthetic chemistry and good ligands in the organometallic complexes.This dual character makes olefins a rich source of chiral ligands and catalysts for asymmetric catalysis.Herein,we willbriefly summarize our studies on the development of chiral diene ligands for transition-metal catalyzed asymmetric reactions and chiral FLP catalysts for asymmetric metal-free hydrogenations and hydrosilylations.Several acyclic chiral diene ligands as well as P/olefin and S/olefin hybrid ligands were developed for Rh or Pd-catalyzed asymmetric reactions.With these ligands in hand,we further put forward a novel strategy for acquiring chiral FLP catalysts via the in situ hydroboration of chiral dienes with Piers'borane.These catalysts proved to be highly ffective for asymmetric metal-free hydrogenations and hydrosilylations of imines,ilyl enol ethers,ketones,and aromatic N-heterocycles.

Ligand controlled cobalt catalyzed regiodivergent 1,2-hydroboration of 1,3-dienes

Regiodivergent 1,2-hydroboration of 1,3-dienes with pinacolborane has been accomplished by well-defined cobalt complexes of different bidentate ligands. The iminopyridine-cobalt system is selective for Markovnikov 1,2-hydroboration to form allylboronates, while the FOXAP-cobalt(FOXAP=(S)-1-(diphenylphosphino)-2-[(S)-4-isopropyloxazolin-2-yl]ferrocene) catalyst effects the complementary anti-Markonikv 1,2-hydroboration to afford homoallyboronates with high regioselectivity.

Lanthanide complexes mediated coordinative chain transfer polymerization of conjugated dienes

Tremendous advances has been witnessed in the past few years in the lanthanide complexes mediated coordinative chain transfer polymerization(CCTP) of conjugated dienes. CCTP features catalyst economy, well-controlling over both microstructure and architecture of the resulting polymers, and accessibility for novel(co)polymers. This review highlights the recent progresses made in the field of CCTP of dienes. After a brief introduction, the body of this review is divided into three parts:(1) principle of CCTP;(2) coordinative chain transfer homopolymerization of dienes;(3) coordinative chain transfer copolymerization of dienes.At the end, we present some challenges remaining in this area and our personal opinion regarding where this field should continue to develop. CCTP represents a novel strategy to prepare polydiene synthetic rubbers with controlled high molecular weight and narrow molecular weight distribution, which has reached the practical industrial application level, demonstrating a great potential in industrialization.

Ferrocene-containing Polymers Synthesized by Acyclic Diene Metathesis(ADMET)Polymerization

Herein we reported that ferrocene-containing polymers could be synthesized via acyclic diene metathesis （ADMET） polymerization of ferrocene-containing bis-styryl monomers. The all-trans-configured vinylene bonds of stilbene segment were proven by means of ^13C-NMR, ^1H-NMR, MALDI-TOF mass spectrometry and FTIR. Poly（1） showed maxima for absorption at 320 nm and emission at 430 nm which are structurally very similar to trans-stilbene, but 24 and 16 nm red shifted respectively. CIE chromaticity diagram shows that emission color could be adjusted by controlling the molecular weight. The polymer showed excellent solubility in common organic solvents and good thermal stability evidenced by TGA and DSC. The results of CV suggested the polymer possessed noninteracting metal centers which was confirmed by a reversible one-electron redox wave observed for the polymer.