Reduction asymetrique catalysee par des complexes de metaux de transition IV. synthese d''amines chirales au moyen d''un complexe de rhodium et d''isopropylidene dihydroxy-2,3 bis(diphenylphosphino)-1,4 butane (diop)

A chiral rhodium complex with (+)-diop as ligand is used as a catalyst in asymmetric synthesis leading to amines and N-acyl derivatives. Two kinds of reactions are investigated: asymetric hydrogenation of enamides and hydrosilylation of imines. Good optical yields are observed in the synthesis of N-acetyl -phnenylethylamine (e.e. 45%) and _N-acetyl -phenylpropylamine (e.e. 83%). A strong solvent effect is observed, which can reverse the absolute configuration of _tN-acetyl--phenylethylamine obtained by reduction of its enamide precursor. N-Benzyl--phenyl ethylamine is prepared by hydrosilylation with 65% optical purity. An asymmetric synthesis of 1,2,3,4-tetrahydropapaverine (e.e 38%) and related compounds is described.     

手性螺-环丙烷化合物中手性辅基的区域性转换反应的研究

通过串联的不对称双Michael加成/分子内亲取代反应,一举得到了具有四个新手性中心的螺环/环丙烯类化合物(4).4在丙酮-5%HCl溶液中50℃下发生区域选择性单水解转换反应,得到螺[1-溴-4-羟基-5-氧杂-6-氧代双环[3.3.0]已-2,3'-(4'-亲核氧基-5'-孟氧基丁内酯)](5),化学产率53%～69%,光学纯度d.e≥98%.4在甲醇/TsOH催化下,实现了区域选择性单醇解转换反应,得到螺[1-溴-4-甲氧基-5-氧杂-6-氧代双环[3.1.0]已烷-2,3'-(4'-亲核氧基-5'-孟氧基丁内酯)](6),化学产率50%～78%,光学纯度d.e.≥98%.经元素分析,[α]D^20,UV,IR,1^HNMR,13^CNMR,MS以及X射线四圆衍射测定,确认了它们的化学结构。     

Asymmetric cyclization of 2-alkenylphenols. A comparative study on the use of palladium(II) and titanium(IV) complexes

The oxidative cyclization of 2-(3-pentenyl)phenol catalyzed by [(η³-pinene)PdOAc]₂ gives optically active (+)-2-vinylchroman (25% e.e.), while (−)-2-(1-hydroxyethyl)chroman (56% e.e.) is formed as a single diastereomer upon treatment with t-BuOOH in the presence of Ti(OⁱPr)₄ and -(+)-diethyl tartrate. 2-(2-Butenyl)phenol also undergoes the Ti-promoted asymmetric cyclization to give (2S,1′R)-(−)-2-(1-hydroxyethyl)-2,3-dihydrobenzofuran (29% e.e.).     

Single and double asymmetric induction in Diels-Alder cycloadditions with chiral acylnitroso dienophiles

Diels-Alder reaction of the achiral 1-silyloxybutadiene 1a with the chiral acyinitroso dienophile 2a gave cycloadduct 4 in high diastereomeric excess (d.e. > 98 %), a result which is undoubtedly due to the C-2 symmetrical chiral dimethylpyrrolidine inductor. Excellent d.e. was also observed when the (R)-prolinol dienophile 2d was reacted with the chiral diene 1b (d.e. = 96 %), whereas cycloaddition of the (S) enantiomer 2e with 1b gave only poor asymmetric induction (d.e. = 4 %). These two latter examples nicely illustrate the influence of “matched pair” (1b/2d) versus “mismatched pair” (1b/2e) upon double asymmetric induction. All herein reported Diels-Alder cycloadditions were regiospecific.     

Synthesis and biological activities of novel chiral fluorinated β‐carboline derivatives

A series of unreported chiral β‐carbolines 4 with trifluoromethyl group at position‐1 and chiral carboxamide chains or amino acid ester chains at position‐3 has been designed and synthesized. The results of bioassay in vitro show that compounds 4e, 4i and 4k show 78.8%, 84.0% and 78.9% inhibition on monoamine oxidase, in 1 mmol/L, respectively, and compound 4e also exhibit 60.9% inhibitory activity on tumor lung cell A‐549 in 10^?5 mmol/L. In view of different configuration, the inhibitory activity on monoamine oxidase of S‐enantiomer of the target compound is better than that of R‐enantiomer.     

Asymmetric deprotonation—substitution of arenetricarbonylchromium(0) complexes: substituent controlled lithiation with the butyllithium–sparteine system

Attempted enantioselective deprotonation of fluorobenzenetricarbonylchromium(0) with ca. 1 equivalent of butyllithium/(−)-sparteine in ether–hexane at −78°C followed by a chlorotrimethylsilane quench gave the racemic ortho-substituted product. Analogous enantioselective deprotonation of anisoletricarbonylchromium(0), followed by electrophilic quench, gave the 1-(Rp)-substituted complexes in up to 77% yield with 27% e.e., but with methoxymethoxybenzenetricarbonylchromium(0), (4-triisopropylsilyloxymethyl)methoxymethoxybenzenetricarbonylchromium(0) and (N-t-butoxycarbonylaniline)tricarbonylchromium(0), the 1-(Sp)-products were formed in up to 58% yield with 92% e.e. The results are explained in terms of coordinative and non-coordinative enantioselective lithiation.     

Anion and ion-pair receptor chemistry: highlights from 2000 and 2001

This review article highlights advances made in abiotic anion coordination chemistry in 2000 and 2001. The structure of this review is that similar to the previous reviews in this series that covered 1997, 1998 and 1999 [1 and 2]. The review also includes examples of ion-pair receptors. The first section examines anion receptors that do not contain metal ions. This is followed by a review of metal containing anion receptors in which the metal can function as: (i) a coordination site for the anion; (ii) an agent withdrawing electron density from the receptor; (iii) an organisational element in the receptor; (iv) a sensor; and (v) a co-bound guest in ion-pair receptor. Examples of the role of anions in directing the self-assembly of complex molecular architectures are presented in the final section.     

Cationic polymerization of 2-vinyl-1,3-dioxane

The cationic polymerization of 2-vinyl-1,3-dioxane initiated with triethyloxonium tetrafluoroborate was studied with particular emphasis on elucidation of the structure of the polymer. The polymer was a light yellow powdery material with a molecular weight of several thousands which was soluble in most organic solvents. The infrared and NMR investigations on the polymer, together with chemical analyses, showed that the polymer consisted of the three structural units I, II, and III, the contents of which were estimated to be 5–10%, 20–25%, and 65–70%, respectively. The formation of the structural units I and II was discussed in detail.     

A Rapid and Facile Synthesis of Nanofibrillar Polyaniline Using Microwave Radiation

We present the first fast and facile microwave assisted synthesis of polyaniline (PANI) nanofibers (“MWA synthesis”). Under conventional synthesis (CS), the polymer was produced with 79.7% yield after 5 h at ambient temperature. However, under microwave irradiation, the nanofibers were produced with yield of 76.2% after only 5 min, i.e., with 78.8% after 20 min at ambient temperature. The FTIR and Raman spectra show the PANI structure in all samples either synthesized conventionally or in the microwave. SEM and TEM confirm the nanofibrillar morphology.

     

Inside Back Cover: Cu(II)‐Catalyzed Ligand‐Free Oxidation of Diarylmethanes and Second Alcohols in Water (Chin. J. Chem. 9/2017)

The inside back cover picture shows a simple and efficient Cu(II )‐catalyzed ligand‐free oxidation of diarylmethanes and secondary alcohols using 70% TBHP in water. A series of diarylmethanes were directly oxidized into diaryl ketones in 67%–98% yields. Additionally, various secondary alcohols were also transformed into the desired products in 48%–98% yields. Importantly, the catalytic system in the absence of any organic solvent, surfactant, or phase transfer agent, had a wide substrate scope and a high tolerance for various functional groups. More details are discussed in the article by Liu et al. on page 1391–1395.

     

HPW and supported HPW catalyzed condensation of aromatic aldehydes with aniline: Synthesis of DATPM derivatives

The mesoporous Si-MCM-41 was synthesized by hydrothermal method and various wt.% (20 and 30 wt.%) of HPW were loaded on Si-MCM-41 by wet impregnation method. The synthesized Si-MCM-41 and HPW-loaded catalysts were characterized by XRD, BET surface area, FT-IR, TEM and TGA–DTG techniques. The catalytic activity of the catalyst was tested over the condensation reaction of aniline with various aromatic aldehydes at refluxing temperature under liquid-phase condition, which yields highly commercial product namely diamino triphenyl methanes (DATPMs). The effects of various parameters like catalyst, mole ratio, solvents and substituent effect on the formation of DATPMs were optimized. The catalytic activity of the catalysts showed the following order: H₃PW₁₂O₄₀·nH₂O > H₃PMo₁₂O₄₀·nH₂O > H₄SiW₁₂O₄₀·nH₂O > 20 wt.% HPW/MCM-41 > 30 wt.% HPW/MCM-41 > HM (12) > Hβ (8) > HY (4) > HZSM-5 (15) > Al-MCM-41 (25). The results showed that mole ratio of 4:1 (aniline:aldehyde) gave higher yield than the other mole ratios. Acetonitrile and ethyl acetate shows better activity especially in the supported materials than toluene was used as a solvent. The product thus obtained was analyzed by ¹H NMR, FT-IR techniques.     

A simple procedure for the synthesis of benzoxanthene derivatives under microwave irradiation conditions

A rapid and efficient method is developed to synthesize a series of benzoxanthene derivatives by the reaction of aldehydes and 2‐hydroxynaphthalene‐1,4‐dione in mixed solvent of acetic acid and ethylene glycol under microwave irradiation. The method has the advantages of short synthetic route, operational simplicity and higher yields (70%～85%).     

Optically active phenanthrolines in asymmetric catalysis. IV. Enantioselective hydrosilylation of acetophenone by rhodium/chiral alkyl phenanthroline catalysts.

The in situ catalysts prepared from [Rh(Cod)Cl]₂ (Cod = 1,5-cyclooctadiene) and chiral alkylphenanthroline ligands 1–6 display a remarkable activity in the asymmetric hydrosilylation of acetophenone affording, after hydrolysis, the expected 1-phenylethanol in high yield and complete selectivity. High enantioselectivities, up to 76%, were obtained in the presence of 2-substituted derivatives 5 and 6, whereas 3-alkylphenanthrolines 1–4 gave e.e.'s not higher than 6%. High chemical yields, but modest enantioselectivities (10–20% e.e.) were recorded with the potentially terdentate ligands 7–10. Chiral alkylphenanthrolines were poorly efficient ligands in the asymmetric Ni-catalysed cross-coupling of -methylbenzylmagnesium chloride with vinyl bromide.     

Crystallisation induced resolution of 4-fluorophenylglycine

4-Fluorophenylglycine 1 is resolved to 99.0% e.e. and 65% overall yield via its methyl ester 2 using a crystallisation induced resolution.     

Water Storage in Thin Films Maintaining the Total Film Thickness as Probed with in situ Neutron Reflectivity

We investigate a new type of thin film material which allows for water storage without an increase in film thickness, whereas typically water storage in polymers and polymer films is accompanied with a strong swelling of the film, i.e., a strong increase in the film thickness. So these films will avoid problems related to strains which are caused by swelling. The basic key for the preparation of such thin films is the installation of a glassy network by the use of an asymmetric diblock copolymer polystyrene‐block‐poly(N‐isopropylacrylamide) [P(S‐b‐NIPAM)] with a long PS and short PNIPAM block in combination with a solvent which is more equal in interaction with both the blocks as compared to water. With in situ neutron reflectivity the water storage and removal are probed. The total film thickness increases only by 2.5% by allowing for a total water storage of 17.4%. Thus the material can be used for coatings to reduce humidity in nano‐applications, which might suffer from changes in the water content of the surrounding environment.

     

Impact fracture mechanisms in polymer blends: Rubber-toughened nylon

The impact fracture mechanisms of rubber-toughened nylon are analyzed by measuring the energy dissipated in several different processes during notched fracture. An energy balance is thus established for the impact fracture. The stress-whitened zone is shown to be the energy dissipation zone, having an energy dissipation density of 5.30 cal/g. About 25% (i.e., 1.44 cal/g) of the impact energy is dissipated by matrix crazing. About 75% (i.e., 3.86 cal/g) is dissipated as heat by matrix yielding, causing a temperature rise of 9.1 °C in the energy dissipation zone. Surface energy storage on the fracture surfaces is negligible (i.e., 1.45 × 10^?5 cal/g). During matrix yielding, about 12% of α-triclinic nylon crystals is transformed into pseudohexagonal crystals.     

Directed metalation/ligand coupling approach to the enantioselective synthesis of 1,1′-binaphthyls

Introduction of a 2-isopropoxycarbonyl or 2-NN-dimethylcarbamoyl group into homochiral 1-p-tolyl- or 1-t-butyl-sulfinylnaphthalenes, via directed metalation reaction, followed by ligand coupling reaction with 1-naphthylmagnesium bromide, furnished atropisomeric 1,1′-binaphthyls in 82–95% enantiomeric excess (e.e.).     

The Silane‐ene and Silane‐Acrylate Polymerization Process: A New Promising Chemistry?

The combination of silanes and enes yields highly reactive photopolymerizable mixtures that exhibit very low oxygen sensitivity. Diphenylsilane (SiH) has been used in combination with different multifunctional acrylates (AC) and conversions of 100% and about 25% for AC and SiH, respectively, have been reached. Final tack free polymers are obtained as a consequence of the fact that the polymerization rates are not affected by oxygen. When using vinylacetate (VA), divinylether (DVE), and allylether (AE) units, the final silane conversion still remains low (50, 20, and 20%, respectively) but are promising. The reactivity of the silyl radicals is investigated by laser flash photolysis. The role of the bond dissociation energy of the silane is outlined.

     

Back Cover: Highly Efficient Photocatalytic Remediation of Simulated Polycyclic Aromatic Hydrocarbons (PAHs) Contaminated Wastewater under Visible Light Irradiation by Graphene Oxide Enwrapped Ag3PO4 Composite (Chin. J. Chem. 10/2017)

The back cover picture shows a photocatalytic remediation of polycyclic aromatic hydrocarbons (PAHs) from wastewater with graphene oxide (GO) enwrapped silver phosphate as visible light‐driven photocatalysts. PAHs are a class of highly mutagenic and carcinogenic organic pollutants that pose serious threats to human health and the ecosystem. GO/Ag₃PO₄ was synthesized by a simple precipitation method. The photocatalysts exhibited superior photocatalytic activity and stability. The degradation efficiency of naphthalene, phenanthrene and pyrene could reach 49.7%, 100.0% and 77.9%, respectively within 5 min irradiation. Meanwhile, the efficiencies of 44.6%, 95.2% and 83.8% were achieved for naphthalene, phenanthrene and pyrene degradation even after 5 times of recycling in the GO/Ag₃PO₄‐PAHs photocatalysis system. More details are discussed in the article by Bao et al. on page 1549–1558.

     

Photoinduced Acrylate Polymerization: Unexpected Reduction in Chain Branching

The branching stemming from midchain radical formation in n‐butyl acrylate polymerization is investigated via melt‐state ¹³C NMR measurements. The dependence of the degree of branching (DB) on the monomer conversion of the system is examined for photoinduced polymerizations, revealing a steady increase in branching with conversion. For polymerization at moderate light intensities, an increase in branching from 0.03% to 0.37% is observed for polymerizations at 60 °C, which is fivefold below the level of branching observed in thermally initiated poly­merizations under otherwise identical reaction conditions. The reason for this overall reduction in branching remains momentarily unclear; yet, a strong dependence of branching on light intensity is observed. While polymerization under a 1 W LED lamp results at almost full monomer conversion in branching degrees of 0.22%, polymerization under a 400 W lamp yields 1.81% of chain branches.