低价钛引起的酰氯与脂肪酮的还原偶联反应

在低价钛(TiCl4-Zn)试剂作用下, 酰氯与两分子脂肪酮发生分子间交叉还原偶联反应生成烯烃3。     

Calcium Borohydride

Calcium borohydride reduces both aliphatic and aromatic esters to alcohols completely in the presence of alkene catalysts. The intermediate borates formed during the reduction of aromatic esters are converted to aldehydes with aqueous NaOC1 in good yields.     

TMSCl-promoted selective oxidation of sulfides to sulfoxides with hydrogen peroxide

Selective oxidation of sulfides to sulfoxides is achieved using H₂O₂ and TMSCl as the promotor. Aromatic and aliphatic sulfides are oxidized to sulfoxides in excellent yields and in short reaction times. Different functional groups including ketone, alkene, ester, and alcohol are tolerated.     

Enamines: efficient nucleophiles for the palladium-catalyzed asymmetric allylic alkylation

Enamines were tested to be efficient nucleophiles for palladium-catalyzed asymmetric allylic alkylation, avoiding the use of unstablilized ketone enolates formed by strong bases. The influence of the chiral metallocene-based ligands upon this reaction was studied in detail. It was shown that planar chirality played an important role in enantioselectivities. Meanwhile, different kinds of enamines and allylic acetate to the reactions were also investigated. High catalytic activity and excellent enantioselectivity (up to 99% ee) were obtained with pyrrolidine enamines of both aliphatic and aromatic ketone.     

A RuH(2)(CO)(PPh(3))(3)-catalyzed regioselective arylation of aromatic ketones with arylboronates via carbon-hydrogen bond cleavage

When the reaction of aromatic ketones with arylboronates (arylboronic acid esters) using RuH(2)(CO)(PPh(3))(3) (3) as a catalyst was conducted in toluene, the corresponding arylation product was obtained in moderate yields. In this case, a nearly equivalent amount of a benzyl alcohol derived from a reduction of an aromatic ketone was also formed. The use of aliphatic ketones, such as pinacolone and acetone, as an additive or a solvent dramatically suppressed the reduction of the aromatic ketones and, as a result, ortho-arylation products were obtained in high yield based on the aromatic ketones. In these reactions, the aliphatic ketone functioned as a scavenger of ortho-hydrogens of the aromatic ketones and the B(OR)(2) moiety of the arylboron compound (HB species). A variety of aromatic ketones, such as acetophenones, acetonaphthones, tetralones, and benzosuberone, could also be used in this coupling reaction. Several arylboronates containing electron-donating (NMe(2), OMe, and Me) and -withdrawing (CF(3) and F) groups were also applicable to this coupling reaction. Intermolecular competitive reaction using pivalophenone-d(0)() and -d(5) and intramolecular competitive reaction using pivalophenone-d(1) were carried out using 3 as a catalyst. The k(H)/k(D) value for the intermolecular competitive reaction was substantially different, compared with intramolecular competitive reaction. This strongly suggests the production of an intermediate where the ketone carbonyl is coordinated to the ruthenium involved in this catalytic reaction. (1)H and (11)B NMR studies using 2'-methylacetophenone, phenylboronate (2), and pinacolone (6) indicate that 6 functions effectively as a scavenger of the HB species.     

Simple route to new oxadiazaboroles and oxadiazoles via amidoximes

Abstract

The novel push–pull alkene, the 2-(nitro-nitrosomethylene)-pyrrolidine with numerous aliphatic or aromatic amines as nucleophiles afforded amidoximes. Various substituted oxadiazaborole and oxadiazole derivatives were prepared starting from these amidoximes, widening the synthetic applicability of the push–pull alkenes. Acylation of the amidoximes was also examined. The mechanism of the amidoxime formation was investigated by computational methods.     

Enantioselective cyanosilylation of ketones by a catalytic double-activation method with an aluminium complex and an N-oxide

Double-activation catalysis promises high catalytic efficiency in the enantioselective cyanosilylation of ketones through the combined use of a Lewis acid and a Lewis base. Catalyst systems composed of a chiral salen-Al complex and an N-oxide have high catalytic turnovers (200 for aromatic ketones, 1000 for aliphatic ones). With these catalysts, a wide range of aliphatic and aromatic ketones were converted under mild conditions into tertiary cyanohydrin O-TMS ethers in excellent yields and with high enantioselectivities (94% ee for aromatic ketones, 90% ee for aliphatic ones). Preliminary mechanistic studies revealed that the salen-Al complex played the role of a Lewis acid to activate the ketone and the N-oxide that of a Lewis base to activate TMSCN; that is, double activation.     

An unexpected directing effect in the asymmetric transfer hydrogenation of α,α-disubstituted ketones

α,α-Disubstituted ketones containing an aromatic ring or alkene are reduced in high enantiomeric excess using an asymmetric transfer hydrogenation catalyst. The sense of reduction indicates that the unsaturated region of the ketone adopts a position adjacent to the Ru-bound η(6)-arene ring in the reduction transition state.     

苦碟子挥发油化学成分的分析

对我国东北地产苦碟子中挥发油成分进行系统分析,确定挥发油的化学成分,为阐述其生物活性提供依据.采用水蒸汽蒸馏法提取挥发油,气相色谱--质谱联用仪进行分析.结果鉴定出37种化合物.在这些化合物中,脂肪烷烃类占53.21%,酮、醛类占39.05%,烯、烯醇、烯酸类占4.94%,酯类占1.57%.其挥发油的主要成分是6,10,14-三甲基-2-十五烷酮,含量为33.98%.     

Aluminum enolates via retroaldol reaction: catalytic tandem aldol-transfer—Tischtschenko reaction of aldehydes with aldol adducts of ketones to ketones

Bidentate aluminum chelates derived from biphenol, binaphthol and catechol were found to be efficient catalysts for aldol-transfer reactions of ketone to ketone aldol adducts with aliphatic or aromatic aldehydes giving rise to the formation of aldol adducts of ketones to the aldehydes. In the presence of an excess of an aliphatic aldehyde, a catalytic tandem aldol-transfer—Tischtschenko reaction is observed. The tandem reaction produces monoesters of 1,3-diols with high anti selectivity and with modest to good chemical yield. 1,2-Unsaturated aldehydes are less reactive in the aldol-transfer reaction and require 2-4 times higher load of the catalyst to be used than aliphatic and aromatic aldehydes. Poor diastereoselectivity was observed in the formation of α-substituted aldols and 2-substituted monoesters of anti-1,3-diols indicating that the aldol-transfer reaction is not diastereoselective with the catalysts studied. The utility of the highly 1,3-anti selective formation of diolmonoesters was found to be limited by acyl migration.     

An efficient synthesis of 2-amino alcohols by silica gel catalysed opening of epoxide rings by amines

Silica gel (60-120 mesh) efficiently catalyses the opening of epoxide rings by amines at rt under solvent-free conditions providing an easy method for the synthesis of 2-amino alcohols. Aromatic and aliphatic amines react with cyclohexene oxide with exclusive formation of the trans-2-aryl/alkylaminocyclohexanols in high yields. A complementary regioselectivity is exhibited by aromatic and aliphatic amines during the reaction with styrene oxide. The epoxide ring of non-styrenoidal unsymmetrical alkene oxide undergoes selective nucleophilic attack at the sterically less hindered carbon by aniline.     

Covalent bonding of alkene and alkyne reagents to graphitic carbon surfaces

Various aromatic and aliphatic alkynes and one alkene were covalently bonded to sp(2)-hybridized carbon surfaces by heat treatment in an argon atmosphere. X-ray photoelectron spectroscopy, Raman, and FTIR spectra of the modified surfaces showed that the molecules were intact after the 400 degrees C heat treatment but that the alkyne group had reacted with the surface to form a covalent bond. Alkynes with ferrocene and porphyrin centers exhibited chemically reversible voltammetric waves that could be cycled many times. Atomic force microscopy of the modified surfaces indicated a thickness of the molecular layer consistent with monolayer coverage, and surface coverage determined by voltammetry was also in the monolayer range. Raman spectroscopy of the porphyrin monolayers formed from a porphyrin alkyne showed no evidence for dimer formation, although multilayer formation may occur at undetected levels. FTIR spectra of the porphyrin-modified carbon surfaces were well-defined, similar to the parent molecule, and indicative of an average tilt angle between the porphyrin plane and the surface normal of 37 degrees . The bond between the molecular monolayer and the carbon surface was quite stable, withstanding sonication in tetrahydrofuran, mild aqueous acid and base, and repeated voltammetric cycling in propylene carbonate electrolyte. Heat treatment of alkynes and alkenes appears to be a generally useful method for modifying carbon surfaces, which can be applied to both aromatic and aliphatic molecules.     

The effect of incorporation of ferrous titanate nanoparticles in sulfonated poly(ether ether ketone)/poly (amide imide) acid-base polymer for cations exchange membrane fuel cells

Journal of Solid State Electrochemistry - The sulfonated poly(ether ether ketone) (SPEEK) is one of the most promising aromatic proton exchange polymer membranes concerning fluorinated aliphatic...     

Direct intermolecular hydroacylation of N,N-dialkylacrylamides with aldehydes catalyzed by a cationic rhodium(I)/dppb complex

[structure: see text]. A cationic rhodium(I)/dppb complex catalyzed direct intermolecular hydroacylation of N,N-dialkylacrylamides with both aliphatic and aromatic aldehydes has been achieved through the stabilization of acylrhodium intermediates by alkene chelation to rhodium. This method represents a versatile new route to gamma-ketoamides in view of the high atom economy and commercial availability of substrates.     

Gold-Catalyzed C−H Functionalization Polycondensation for the Synthesis of Aromatic Polymers

Homogeneous gold (Au) complexes have demonstrated tremendous utility in modern organic chemistry; however, their application for the synthesis of polymers remains rare. Herein, we demonstrate the first catalytic application of Au complexes toward the polycondensation of alkyne-containing comonomers and heteroarene nucleophiles. Polymerization occurs through successive intermolecular hydroarylation reactions to produce high molecular weight aromatic copolymers with 1,1-disubstituted alkene backbone linkages. Clear correlations between the rate and degree of polymerization (DP) were established based on catalyst structure and counterion pairing, thus enabling polymerization reactions that proceeded with remarkable efficiency, high reactivity, and exceptional DPs. The reactivity is broad in scope, enabling the copolymerization of highly functionalized aromatic and aliphatic monomers. These results highlight the untapped utility of Au catalysis in providing access to new macromolecular constructs.     

The construction of quaternary stereocenters by the Henry reaction: circumventing the usual reactivity of substituted glyoxals

The enantioselective Henry reaction between alkyl‐ and arylglyoxal hydrates and nitromethane catalyzed by Cu^II–iminopyridine complexes takes place regioselectively on the ketone carbonyl group to give chiral tertiary nitroaldols with high functional group density and enantiomeric excesses of up to 96 %. Both aromatic and aliphatic glyoxals are suitable substrates for this reaction.     

Stereoselective ketone reduction by a carbonyl reductase from Sporobolomyces salmonicolor. Substrate specificity, enantioselectivity and enzyme-substrate docking studies

In our effort to search for effective carbonyl reductases, the activity and enantioselectivity of a carbonyl reductase from Sporobolomyces salmonicolor have been evaluated toward the reduction of a variety of ketones. This carbonyl reductase (SSCR) reduces a broad spectrum of ketones including aliphatic and aromatic ketones, as well as alpha- and beta-ketoesters. Among these substrates, SSCR shows highest activity for the reduction of alpha-ketoesters. Aromatic alpha-ketoesters are reduced to (S)-alpha-hydroxy esters, while (R)-enantiomers are obtained from the reduction of aliphatic counterparts. This interesting observation is consistent with enzyme-substrate docking studies, which show that hydride transfer occurs at the different faces of carbonyl group for aromatic and aliphatic alpha-ketoesters. It is worthy to note that sterically bulky ketone substrates, such as 2'-methoxyacetophenone, 1-adamantyl methyl ketone, ethyl 4,4-dimethyl-3-oxopentanoate and ethyl 3,3-dimethyl-2-oxobutanoate, are reduced to the corresponding alcohols with excellent optical purity. Thus, SSCR possesses an unusually broad substrate specificity and is especially useful for the reduction of ketones with sterically bulky substituents.     

Zirconium–BINOLate-catalyzed,enantioselective aldol-Tishchenko reactions of aromatic ketone aldols

3,3′-Substituted BINOL’s have been identified as suitable chiral ligands for the zirconium-catalyzed aldol-Tishchenko reaction of aromatic ketone aldols with aliphatic aldehydes. 1,3-anti-Diol monoesters were obtained in excellent yields, complete anti-diastereocontrol, and enantioselectivities of up to 60% ee.     

Ferrous methanesulfonate as an efficient and recyclable catalyst for chemoselective synthesis of 1,1-diacetate from aldehydes

Ferrous methanesulfonate catalysing the conversion of aromatic,heteroaromatic,unsaturated,and aliphatic aldehydes to 1,1- diacetates at room temperature under solvent-free condition has been developed.The catalytic activity of seventeen metal methanesulfonates was compared under the same condition,ferrous methanesufonate proved to be the best.It can be easily recovered and reused for several times without distinct deterioration in catalytic activity.During the competitive protection between a ketone and ...     

Asymmetric hydrogenation of di and trisubstituted enol phosphinates with N,P-ligated iridium complexes

The iridium-catalyzed asymmetric hydrogenation of various di- and trisubstituted enol phosphinates has been studied. Excellent enantioselectivities (up to >99% ee) and full conversion were observed for a range of substrates with both aromatic and aliphatic side chains. Enol phosphinates are structural analogues of enol acetates, and the hydrogenated alkyl phosphinate products can easily be transformed into the corresponding alcohols with conservation of stereochemistry. We have also hydrogenated, in excellent ee, several purely alkyl-substituted enol phosphinates, producing chiral alcohols that are difficult to obtain highly enantioselectively from ketone hydrogenations.