Sulfuric Acid Adsorbed on Silica Gel. A Multipurpose Acid Catalyst

A series of acid catalyzed reactions like the dehydration of alcohols, conversion of ketones to 1,3-dioxolanes and their hydrolysis, α,β-unsaturated ketones to enol ethers, and alcohols to methyl-methoxyethyl ethers are performed efficiently in high yield with sulfuric acid adsorbed on silica gel as catalyst.     

Thermodynamic favorable CO2 conversion via vicinal diols and propargylic alcohols: A metal-free catalytic method

Organocatalysis represents a promising field in chemical fixation of CO2.Herein,a facile metal-free strategy was reported for the one-pot preparation of cyclic carbonates and a-hydroxy ketones from vicinal diols,propargylic alcohols and CO2.Wide scope of vicinal diols and propargylic alcohols was demonstrated to be efficient under the DBU-catalyzed conditions.A plausible mechanism was proposed,which included detailed main and side reactions under the metal-free conditions.     

高分子载体Lewis酸催化剂聚苯乙烯-四氯化钛复合物

交联聚苯乙烯白球(含DVB 5～7%)在CS₂中与TiCl₄反应可形成一种稳定的复合物,其含氯量为4.5%。这种复合物不怕水,在空气中放置一年以上不失效。这种高分子载体Lewis酸催化剂可作为酯化、缩醛、缩酮、成醚和付氏烷基化等有机合成反应的良好催化剂,还可重复使用4—5次。     

A green chemistry approach to a more efficient asymmetric catalyst: solvent-free and highly concentrated alkyl additions to ketones

There is a great demand for development of catalyst systems that are not only efficient and highly enantioselective but are also environmentally benign. Herein we report investigations into the catalytic asymmetric addition of alkyl and functionalized alkyl groups to ketones under highly concentrated and solvent-free conditions. In comparison with standard reaction conditions employing toluene and hexanes, the solvent-free and highly concentrated conditions permit reduction in catalyst loading by a factor of 2- to 40-fold. These new conditions are general and applicable to a variety of ketones and dialkylzinc reagents to provide diverse tertiary alcohols with high enantioselectivities. Using cyclic conjugated enones, we have performed a tandem asymmetric addition/diastereoselective epoxidation using the solvent-free addition conditions followed by introduction of a 5.5 M decane solution of tert-butyl hydroperoxide (TBHP) to generate epoxy alcohols. This one-pot procedure allows access to syn epoxy alcohols with three contiguous stereocenters with excellent enantio- and diastereoselectivities and high yields. Both the solvent-free asymmetric additions and asymmetric addition/diastereoselective epoxidation reactions have been conducted on larger scale (5 g substrate) with 0.5 mol % catalyst loadings. In these procedures, enantioselectivities equal to or better than 92% were obtained with isolated yields of 90%. The solvent-free and highly concentrated conditions are a significant improvement over previous solvent-based protocols. Further, this chemistry represents a rare example of a catalytic asymmetric reaction that is highly enantioselective under more environmentally friendly solvent-free conditions.     

9,10-二氰基蒽光敏夺氢反应的研究

本文研究了缺电子敏化剂9,10-二氰基蒽(DCA)对苄醇类化合物(二苯甲醇、苯甲醇)及甲苯类化合物(甲苯、对-二甲苯)的光敏化夺氢反应,证明上述两类反应是经由两种不同机制进行的。     

Metal-assisted reactions—12 : Unusual selectivity in the reduction of ketones with zinc or cadmium bis-tetrahydroborate/dimethylformamide complex

Zinc bis-tetrahydroborate forms a solid complex with dimethylformamide (DMF) of composition, Zn(BH₄)₂ 1.5DMF. Unlike zinc bis-tetrahydroborate itself, the complex with DMF can be stored as a solid at room temperature. Ketones and aldehydes are reduced to the corresponding alcohols by the complex but the mechanism of reduction appears to be different from that using zinc bis-tetrahydroborate itself and from other tetrahydroborates in that only one hydride equivalent from each BH₄⁻ unit is utilized and not four. Further, although saturated aliphatic ketones are reduced rapidly to alcohols, aromatic ketones react much more slowly and ,β-unsaturated ketones react very slowly so that the complex appears to have selective reducing potential with regard to different classes of ketones. It is also apparent that the zinc bis-tetrahydroborate/DMF complex reduces sterically hindered saturated ketones much more slowly than it does unhindered ketones. An analogous cadmium bis-tetrahydroborate/DMF complex can be prepared in solution and reacts with ketones similarly to the zinc complex.     

Photoinduced Electron Transfer from Xanthates to Acyl Azoliums: Divergent Ketone Synthesis via N-Heterocyclic Carbene Catalysis

Considering the prevalence of alcohols and carboxylic acids, their fragment cross-coupling reactions could hold significant implications in organic synthesis. Herein, we report a versatile method for synthesizing a diverse range of ketones from alcohols and carboxylic acid derivatives via N-heterocyclic carbene (NHC) catalysis. Mechanistic investigations revealed that photoexcited xanthates and acyl azoliums undergo single electron transfer (SET) under photocatalyst-free conditions, generating NHC-derived ketyl radicals and alkyl radicals. These open-shell intermediates subsequently undergo the radical-radical cross-coupling reaction, yielding valuable ketones. Furthermore, this approach can be employed in three-component reactions involving alkenes and enynes, resulting in structurally diverse cross-coupled ketones. The unified strategy offers a unique opportunity for the fragment coupling of a diverse range of alcohols and carboxylic acid derivatives, accommodating diverse functional groups even in complex settings.     

Calcium alkoxyalanates : III. Reduction of organic functional groups by calcium tetrakis(alkoxy)alanates

Calcium tetrakis(alkoxy)alanates obtained from different alcohols reduce aldehydes, ketones, acids, esters, acid chlorides and anhydrides to alcohols in high yields. Good results are achieved in the reduction of amides to amines. The reductions of nitrile and oxime groups and dehalogenation reactions are more difficult. Selectivity is possible in the reduction of organic epoxides.     

Further studies in the acyl-type radical additions promoted by SmI2: mechanistic implications and stereoselective reduction of the keto-functionality

Attempts were made to promote the carbonyl coupling of cyclohexanone to 4-pyridylthioesters of N-carbamate-protected amino acids with the one electron reducing agent, samarium diiodide. Such reactions proved unsuccessful due to the inability of the ketyl-type radical anion intermediate to be reduced to the corresponding dianion at −78°C. Nevertheless, these results explain our recently published work on the high efficiency of the SmI₂-mediated acyl-type radical additions of the same thioesters with electron deficient alkenes [J. Am. Chem. Soc. 2003, 125, 4030]. A study was also undertaken to examine methods for the stereoselective reduction of N-carbamate-protected amino ketones to either the syn- or anti-vicinal amino alcohols. In most cases, LiAl(O-t-Bu)₃H and (S)-Alpine-Hydride were found to effectively provide the anti- and syn-amino alcohols, respectively. The SmI₂-promoted reduction of the same ketones afforded a majority of the syn-isomer with selectivities of approximately 5:1. However, in one case, the SmI₂-promoted reduction was found to be more effective than that of (S)-Alpine-Hydride.     

Catalytic oxidation of alcohols with allyl diethyl phosphate and palladium acetate

Allyl diethyl phosphate (ADP) was found to function as a stoichiometric hydrogen acceptor in a catalytic oxidation reaction of alcohols with Pd(OAc)₂. A variety of acyclic primary and secondary alcohols were oxidized in good yields and under mild conditions to the corresponding aldehydes and ketones, in the presence of Na₂CO₃ or K₂CO₃. Simple aliphatic primary alcohols yielded esters, exclusively. Polar ligand solvents (DMF, DMSO) were found to accelerate the reaction. Slow, but high yield reactions were encountered in THF and acetonitrile as solvents. The reactivity of several other allyl systems serving as H-acceptors, and several Pd compounds serving as catalysts, in the above oxidation reaction, was evaluated. It has been experimentally demonstrated (H-NMR) that ADP is capable of generating a π-allyl-Pd complex using a Pd(0) complex. Consequently, a catalytic cycle was proposed for the above oxidation reaction.     

Electrochemical syntheses in absolute alcohols (Review)

The data on electrosyntheses occurring in absolute aliphatic alcohols, including those involving alcohol molecules, are systematized. Syntheses of alcoholates and phosphoric acid esters, carbonylation, alkoxylation, and electrolyses of ketones and C-H acids in alcohol media are classified with these reactions. Mechanisms of the electrode reactions and their applications are discussed. Ninety references are included.     

Oxidation of non-activated C---H bonds in hydrocarbons and steroids

CrO₃ in CH₂Cl₂/CH₃COOH/(CH₃CO)₂O oxidizes hydrocarbons to alcohols and ketones, 5-androstane and 3β-acetoxy-5-androstane are converted to 5-androst-14-en-16-ones.     

Ruthenium-catalyzed oxidation of alcohols and catechols using t-butyl hydroperoxide

Ruthenium complexes catalyze the oxidation of alcohols to the corresponding ketones or aldehydes when t-BuOOH (70% aq.) is used as an oxidant. The reactions proceed at room temperature to give the products in excellent to fairly good yields. Among the transition metal catalysts used, dichlorotris(triphenylphosphine)ruthenium (RuCl₂(PPh₃)₃) showed the highest catalytic activity. 3,5-Di-t-butylcatechol and 4-t-butylcatechol are also effectively oxidized to the corresponding 1,2-benzoquinones in the presence of a catalytic amount of RuCl₂(PPh₃)₃ at room temperature with 1.1 equiv. of t-BuOOH, in quantitative yields. Hydrogen peroxide (30% aq.) can also be employed as an oxidant to give 1,2-benzoquinones in excellent yields.     

Direct organocatalytic hydroalkoxylation of α,β-unsaturated ketones

The direct addition of a variety of alcohols to in situ activated olefins was observed in the presence of mild bifunctional amine/acid catalysts. Unlike existing methods, the reactions proceed at room temperature and in the absence of transition metals. The use of simple commercially available catalysts, amines and acids makes this an attractive method for the preparation of β-alkoxy ketones, which are prevalent targets and intermediates in organic synthesis.     

Expedient Synthesis of Ketones via N‐Heterocyclic Carbene/Nickel‐Catalyzed Redox‐Economical Coupling of Alcohols and Alkynes†

An N‐heterocyclic carbene/nickel‐catalyzed direct coupling of alcohols and internal alkynes to form α‐branched ketones has been developed. This methodology provides a new approach to afford branched ketones, which are difficult to access through the hydroacylation of simple internal alkenes with aldehydes. This redox‐neutral and redox‐economical coupling is free from any oxidative or reductive additives as well as stoichiometric byproducts. These reactions convert both benzylic and aliphatic alcohols and alkynes, two basic feedstock chemicals, into various α‐branched ketones in a single chemical step.     

Fe2(SO4)3·xH2O CATALYTIC ESTERIFICATION OF MANDELIC ACID WITH ALCOHOLS

Mandelates have played an important role in organic synthesis and are used in artificial flavorings and perfumes. Mandelates may be prepared as follows:1). Direct esterification of mandelic acid with alcohols in the presence of sulfuric acid^1,2 or 2,2-dimethoxypropane and sulfuric acid;³ 2). Treatment mandelic acid and iodide in the presence of sodium hydrogen carbonate;⁴ 3). Treatment mandelic acid and alcohols with thionyl chloride.⁵ But these methods have some advantages and are not universally applicable. For example, the direct esterification catalyzed by sulfuric acid is not suitable for acid sensitive compounds and has the disadvantages of the corrosivity of strong acid and usually accompanying side reactions such as carbonization,oxidation, etherification, etc. We now reported the catalytic esterification of mandelic acid with a serious of alcohols using Fe₂(SO₄)₃·xH₂O as a new convenient catalyst.     

Disparate behavior of ketones and thioketones on reaction with organolithiums

The reactions of alkyllithiums with ketones and thioketones proceed in fundamentally different ways. Whereas alkyllithiums add to the carbonyl carbon of ketones to give tertiary alcohols, the reaction with thioketones proceeds to give secondary thiols by reduction of the CS group. Transition states for the addition and reduction reactions of acetone and thioacetone in ethereal solution have been located and the computed activation free energies are in agreement with the observed behavior of ketones and thioketones in reactions with alkyllithiums.     

An Overview of Selective Oxidation of Alcohols: Catalysts,Oxidants and Reaction Mechanisms

The oxidation of alcohols to carbonyl compounds is one of the most fundamental reactions in synthetic organic chemistry. In order to achieve the realization of dehydrogenation reactions with high atomic efficiency, suitable catalysts and oxidants are considered as the key factors to obtain the optimum activity and aldehydes/ketones selectivity. This review aims to make an overview on the reasonable reaction mechanism and promising catalytic system of alcohols dehydrogenation.     

Organocatalytic asymmetric assembly reactions: one-pot synthesis of functionalized beta-amino alcohols from aldehydes,ketones, and azodicarboxylates

[reaction: see text] l-Proline catalyzed the enzyme-like direct asymmetric assembly of aldehydes, ketones, and azodicarboxylic acid esters to provide optically active beta-amino alcohols. This assembly reaction uses both aldehydes and ketones as donors in one pot. The aldol-derived stereocenter is formed with a reduced facial selectivity in reactions involving (R)-amino aldehydes. The reactions can be performed on a multigram scale under operationally simple and safe conditions without the requirement of an inert atmosphere or dry solvents.