Integrated electrochemical-chemical oxidation mediated by alkoxysulfonium ions

Generation of carbocations by the "cation pool" method followed by reaction with dimethyl sulfoxide (DMSO) gave the corresponding alkoxysulfonium ions. Alkoxysulfonium ions could also be generated by in situ DMSO trapping of electrochemically generated carbocations. The resulting alkoxysulfonium ions were transformed into carbonyl compounds by treatment with triethylamine. The present integrated electrochemical-chemical oxidation can be applied to the oxidation of diarylmethanes to diaryl ketones, toluenes to benzaldehydes, and aryl-substituted alkenes to 1,2-diketones. Moreover, the oxidation of unsaturated compounds bearing a nucleophilic group in an appropriate position gives cyclized carbonyl compounds.     

水介质中无催化剂下醛酮与活泼亚甲基化合物的缩合反应

报道了水相中无催化剂下各种羰基化合物与活泼亚甲基化合物的Knoevenagel缩合反应. 芳香醛与活泼亚甲基化合物如丙二腈、氰基乙酸乙酯、氰基乙酰胺的缩合在室温下即能顺利进行, 获得了很高的收率; 而对于杂环芳醛、α,β-不饱和的醛以及脂肪醛与活泼亚甲基化合物的缩合, 需在50～65 ℃下进行, 也取得了很高的收率; 对于脂肪酮、芳香酮以及二元醛与丙二腈的缩合在75～85 ℃下也能顺利地进行, 获得中等以上的收率. 反应简单、高效而且对环境友好.     

New approach to the synthesis of 1,3-dioxolanes

Application of ethanol to the synthesis of 1,3-dioxolanes by the condensation of carbonyl compounds with vicinal diols results in a high yield of the reaction product and considerably reduces the duration of the process. It is assumed that the effect of the ethanol is caused by the adduct formation with carbonyl compounds (hemiacetals) which behave as active intermediates of the condensation. A cyclic ketal of acetone with glycerol obtained with the help of ethanol was used as a basis component in the synthesis of a series of ketals substituting diol or carbonyl components by transketalyzation mechanism proceeding without water liberation.     

InCl3-catalyzed efficient synthesis of spiro-perimidine derivatives

InCl₃ was found to be a mild and effective catalyst for the simple and efficient synthesis of spiro-perimidine derivatives by the reaction of naphthalene-1,8-diamine and active carbonyl compounds in water at room temperature. This protocol includes some important aspects like the use of water as a “green” reaction medium, good yielding of products and mild reaction conditions.     

氧化脱肟研究新进展

肟是有机合成中一类非常重要且常见的化合物,不仅可用作羰基化合物的保护,而且可通过肟化-脱肟过程对羰基化合物进行分离和纯化。此外,肟还可以由非羰基化合物转变而来,进而通过脱肟反应生成羰基化合物,因此,如何在温和条件下高效实现脱肟反应吸引了人们的广泛关注。目前,已报道的脱肟方法主要包括酸性水解、氧化、还原等。其中,氧化脱肟法,特别是利用过氧化氢或氧气作氧化剂的绿色氧化脱肟方法尤受重视。本文以此为重点,综述了近年来氧化脱肟方法的研究概况和最新进展,并对若干重要的体系作了详细讨论。     

A Mild and Efficient Oxidation of Alcohols in Water

A mild and efficient oxidation of alcohols to the corresponding carbonyl compounds using the PhI(OAc)2 (1.1 eq.) with n-Bu4NBr (8 mol %) in water at room temperature is described.This new procedure is very simple and affords the desired carbonyl compounds in high yields.     

吡哆胺对1,4-二羰基化合物清除机理的密度泛函理论研究

吡哆胺（PM）能够清除生物体新陈代谢过程中产生的活性二羰基化合物,此类化合物能与体内的氨基酸作用生成有毒的吡咯类化合物。本文用密度泛函理论B3LYP方法在6-31G*基组水平上,研究了PM与OPA反应的机理。计算结果表明,该反应可通过两个连续的步骤完成。首先,通过竞争反应生成一个四氢吡咯类化合物;随后,该化合物经过平行反应脱水生成最终产物。理论上,反应过程中还有可能生成亚胺类化合物,但计算结果表明其为副反应。最后,本文讨论了空间位阻效应对反应性质的影响。所有计算结果与实验结果非常吻和。     

Cationic carbohydroxylation of alkenes and alkynes using the cation pool method

The reactions of an N-acyliminium ion pool with alkenes and alkynes gave gamma-amino alcohols and beta-amino carbonyl compounds, respectively, after treatment with H(2)O/Et(3)N. The present reaction serves as an efficient method for cationic carbohydroxylation of alkenes and alkynes. When vinyltrimethylsilane was used as an alkene, the reaction was highly diastereoselective and served as an access to an enantiomerically pure alpha-silyl-gamma-amino alcohol. [reaction: see text]     

Nucleophilic trifluoromethylation of carbonyl compounds and disulfides with trifluoromethane and silicon-containing bases

Provided that DMF (or another N,N-dialkylformamide) is present in the reaction medium, at least in a catalytic amount, fluoroform trifluoromethylates efficiently carbonyl compounds, even enolizable ones, when opposed to (TMS)(2)N(-) M(+), generated in situ from N(TMS)(3) and M(+) F(-) or RO(-) Na(+). When F(-) is used in a catalytic amount, silylated alpha-(trifluoromethyl)carbinols are obtained: in this case, the four-component system HCF(3)/N(TMS)(3)/catalytic F(-)/catalytic DMF behaves like the Ruppert's reagent, especially as far as nonenolizable carbonyl compounds are concerned (CF(3)SiMe(3) remains more efficient for enolizable carbonyl compounds). This process involves an adduct between DMF and (-)CF(3) which is the true trifluoromethylating agent. In the same way, fluoroform efficiently trifluoromethylates disulfides and diselenides when deprotonated with a strong base selected from t-BuOK or N(SiMe(3))(3)/Me(4)NF (or TBAT). t-BuOK is more adapted to the trifluoromethylation of aryl disulfides whereas N(SiMe(3))(3)/F(-) is well suited to that of aliphatic disulfides.     

Amine-catalyzed [3+2] Huisgen cycloaddition strategy for the efficient assembly of highly substituted 1,2,3-triazoles

An enamine-catalyzed strategy has been utilized to fully promote the Huisgen [3+2] cycloaddition with a broad spectrum of carbonyl compounds and azides, thereby permitting the efficient assembly of a vast pool of highly substituted 1,2,3-triazoles. In particular, the employment of commonly used and commercially available carbonyl compounds has resulted in the introduction of a diverse set of functional groups, such as alkyl, aryl, nitrile, ester, and ketone groups, at the 1-, 4-, or 5-positions of the 1,2,3-triazole scaffold. This approach might be manipulated to access more useful and sophisticated heterocyclic compounds. Most significantly, the reaction process exhibits complete regioselectivity, with the formation of only one regioisomer.     

Oxodealkenylative Cleavage of Alkene C(sp3)−C(sp2) Bonds: A Practical Method for Introducing Carbonyls into Chiral Pool Materials

Reported herein is a one‐pot protocol for the oxodealkenylative introduction of carbonyl functionalities into terpenes and terpene‐derived compounds. This transformation proceeds by Criegee ozonolysis of an alkene, reductive cleavage of the resulting α‐alkoxy hydroperoxide, trapping of the generated alkyl radical with 2,2,6,6‐tetramethylpiperidin‐1‐yl (TEMPO), and subsequent oxidative fragmentation with MMPP. Using readily available starting materials from chiral pool, a variety of carbonyl‐containing products have been accessed rapidly in good yields.     

Deoximation of Oximes,Sodium Oximates,and O-Benzoyloximes with Copper (II) Chloride Dihydrate

Oximes, O-benzoyloximes and sodium salt of aldoximes and ketoximes were deoximated to their parent carbonyl compounds with copper (II) chloride dihydrate in acetonitrile as well as water. This method works well with both aldoximes and ketoximes without any risk of overoxidation in the former case. In addition, sensitive groups like ester, acetamido, isolated as well as conjugated carbon-carbon double bond and phenolic and ether linkages could survive the reaction conditions. The yields and reaction rates were increased in case of aromatic oximes when the reaction was carried out in aqueous acetonitrile. A novel deoximation procedure using sodium oximate which showed considerable rate enhancement over that of oximes, and tolerance to hydrolytically labile ester and amide groups is also described.     

Copper catalyzed access to functionalized oxazoles from oximes via carbenoids

An operationally simple, economical and straightforward synthesis of diverse oxazoles from oximes possessing a vicinal carbonyl group has been achieved by treatment of the latter with terminal diazo compounds like ethyl/benzyl diazoacetate and diazoacetophenone (which act as carbenoids) in one pot. At least two reducible functional groups (two ester groups or cyano?+?ester) are simultaneously introduced in one step. This reaction involves expulsion of a molecule each of N₂ and water only as byproducts under copper catalysis. The structure of one of these oxazoles is confirmed by X-ray crystallography. Both the ester groups in the oxazole product could be reduced to alcohol moieties by using NaBH₄/EtOH.     

Reconstructed hydrotalcite as a highly active heterogeneous base catalyst for carbon-carbon bond formations in the presence of water

The aldol reaction of carbonyl compounds is efficiently catalyzed by reconstructed hydrotalcites, obtained by treating the Mg-Al mixed oxide with water, as solid base catalysts in the presence of water. The catalysis of the reconstructed hydrotalcites is attributable to the surface base sites, created during the organization of the layered structure, with uniformly distributed strength. Furthermore, the reconstructed hydrotalcites provide a unique acid-base bifunctional surface capable of promoting the Knoevenagel and Michael reactions of nitriles with carbonyl compounds.     

Amine‐Catalyzed [3+2] Huisgen Cycloaddition Strategy for the Efficient Assembly of Highly Substituted 1,2,3‐Triazoles

An enamine‐catalyzed strategy has been utilized to fully promote the Huisgen [3+2] cycloaddition with a broad spectrum of carbonyl compounds and azides, thereby permitting the efficient assembly of a vast pool of highly substituted 1,2,3‐triazoles. In particular, the employment of commonly used and commercially available carbonyl compounds has resulted in the introduction of a diverse set of functional groups, such as alkyl, aryl, nitrile, ester, and ketone groups, at the 1‐, 4‐, or 5‐positions of the 1,2,3‐triazole scaffold. This approach might be manipulated to access more useful and sophisticated heterocyclic compounds. Most significantly, the reaction process exhibits complete regioselectivity, with the formation of only one regioisomer.     

Catalyst-free conjugated addition of thiols to alpha,beta-unsaturated carbonyl compounds in water

[reaction: see text] Catalyst-free conjugate addition of thiols to alpha,beta-unsaturated carbonyl compounds in water is reported. beta-Sulfido carbonyl compounds were formed at room temperature, in short times and with excellent chemoselectivity. Competitive dithiane/dithiolane formation, transesterification, and ester cleavage were not observed. Water played a dual role in simultaneously activating the alpha,beta-unsaturated carbonyl compound and the thiol. This new methodology constitutes an easy, highly efficient, and green synthesis of beta-sulfido carbonyl compounds.     

Rapid on-plate and one-pot derivatization of carbonyl compounds for enhanced detection by reactive matrix LDI-TOF MS using the tailor-made reactive matrix, 4-dimethylamino-6-(4-methoxy-1-naphthyl)-1,3,5-triazine-2-hydrazine (DMNTH)

In this study, a very sensitive and economical high-throughput methodology has been developed for the analysis of small carbonyl compounds using rapid derivatization with 4-dimethylamino-6-(4-methoxy-1-naphthyl)-1,3,5-triazine-2-hydrazine (DMNTH), a derivatizing agent developed by the Karst group at the University of Münster. DMNTH is highly ionizable by the UV laser and reacts selectively and rapidly with carbonyl moieties. The resulting hydrazone is easily detectable by laser desorption ionization time of flight mass spectrometry (LDI-TOF MS), eliminating the need for the matrix assisted variant (MALDI) and the associated issue of matrix optimization, which greatly simplifies the analysis. It has been demonstrated that a range of carbonyl compounds can be conveniently analyzed by this reactive matrix LDI-TOF MS (RM-LDI-TOF MS) procedure and that furfural DMNThydrazone (prior labeled and labeled in situ) can be used as an internal standard for semiquantitative analysis. Amounts as low as 0.5 ng ml(-1) of 4-methoxybenzaldehyde have been detected using a one-pot derivatization methodology. Rapid on-plate derivatization was also found to be a simple approach for fast and reliable screening of various analytes, although with slightly higher detection limits. To test its applicability in complex matrices, analysis of furfural spiked in beer has been demonstrated. This RM-LDI-TOF MS method shows considerable promise for the analysis of carbonyl compounds in water, particularly for disinfection by-products that result from reaction of natural organic matter with oxidative disinfectants.     

Oxidation of benzylic and some aliphatic alcohols 1,2-ethylenebis(triphenylphosphonium)chlorochromate (EBTPPCC): As a new,an efficient and mild oxidant

1,2-Ethylenebis(triphenylphosphonium)chlorochromate was quantitatively prepared and used for the oxidation of various benzylic and some aliphatic alcohols to their corresponding carbonyl compounds in water or acetonitrile and under microwave irradiation. This new oxidizing agent has advantages over similar oxidants in terms of the amount of used oxidant, short reaction time, simple work-up, and high yields. Furthermore, the oxidation of alcohols occurred under microwave irradiation many times and it produced the corresponding carbonyl compounds with high yields and short reaction times, when compared with the conventional method. Finally, the oxidation of different alcohols were accomplished in water under reflux condition with good yields as green chemistry.     

Cu(II) 2-quinoxalinol salen catalyzed oxidation of propargylic,benzylic, and allylic alcohols using tert-butyl hydroperoxide in aqueous solutions

The synthesis of carbonyl compounds by oxidation of alcohols is a key reaction in organic synthesis. Such oxidations are typically conducted using catalysts featuring toxic metals and hazardous organic solvents. Considering green and sustainable chemistry, a copper(II) complex of sulfonated 2-quinoxalinol salen (sulfosalqu) has been characterized as an efficient catalyst for the selective oxidation of propargylic, benzylic, and allylic alcohols to the corresponding carbonyl compounds in water when in combination with the oxidant tert-butyl hydroperoxide. The reactions proceed under mild conditions (70 °C in water) to produce yields up to 99% with only 1 mol % of catalyst loading. This reaction constitutes of a rare example of propargylic alcohol oxidation in water, and it makes this process greener by eliminating the use of hazardous organic solvents. Excellent selectivity was achieved with this catalytic protocol for the oxidation of propargylic, benzylic, and allylic alcohols over aliphatic alcohols. The alcohol oxidation is thought to go through a radical pathway.     

Epoxidation and oxidation reactions using 1,4-butanediol dimethacrylate crosslinked polystyrene-supported tertiary butyl hydroperoxide

1,4-Butanediol dimethacrylate (1,4-BDDMA) crosslinked polystyrene-supported t-butyl hydroperoxide was employed in the epoxidation of olefins and oxidation of alcohols to carbonyl compounds. The reagent proved to be successful as a recyclable solid phase organic reagent with as much or more efficiency when compared to its monomeric counterpart. The extent of reaction was found to be dependent on various reaction parameters like solvent, temperature, molar concentration and presence of catalyst.