Simple Aliphatic Alcohols Research Articles

Photoredox/persistent radical cation dual catalysis for alkoxy radical generation from alcohols

A mild and general strategy for the direct generation of alkoxy radicals from simple aliphatic alcohols enabled by visible-light-induced photoredox/persistent radical cation dual catalysis is developed.

Unlocking the Friedel-Crafts arylation of primary aliphatic alcohols and epoxides driven by hexafluoroisopropanol

Unlocking the Friedel-Crafts arylation of primary aliphatic alcohols and epoxides driven by hexafluoroisopropanol

The Assignment of the Absolute Configuration of β-Chiral Primary Alcohols with Axially Chiral Trifluoromethylbenzimidazolylbenzoic Acid.

Axially chiral trifluoromethylbenzimidazolylbenzoic acid (TBBA) was used as a chiral derivatization agent for the assignment of the absolute configuration of β-chiral primary alcohols. The structures varied from simple aliphatic alcohols to complex cyclic systems and highly substituted sugar derivatives. The NMR-based method was successfully implemented to evaluate 17 compounds and displayed ΔδPM values higher than 0.1 ppm in most cases, which makes TBBA superior to MTPA and MPA and comparable to 9-AMA.

Enantioselective three-component aminomethylation of \u03b1-diazo ketones with alcohols and 1,3,5-triazines

Enantioselective α-aminomethylation of carbonyl compounds constitutes a powerful protocol for introducing aminomethyl groups to simple organic molecules. However, current strategies rely on nucleophile-based enantioselective activation with inherently activated substrates only, and enantioselective protocol based on the activation of in situ-generated unstable formaldimines remains elusive, probably owing to their unstable nature and the lack of steric environment for efficient stereocontrols. Here, based on a rhodium/chiral phosphoric acid cooperative catalysis, we achieved an enantioselective three-component reaction of α-diazo ketones with alcohols and 1,3,5-triazines. A dual hydrogen bonding between the chiral phosphoric acid catalyst and two distinct active intermediates was proposed to be crucial for the efficient electrophile-based enantiocontrol. A series of chiral β-amino-α-hydroxy ketones including those derived from simple aliphatic alcohols, allylic alcohol, propargyl alcohol, complicated natural alcohols and water could all be prepared in high efficiency and enantioselectivity.

Iron-Catalyzed Borrowing Hydrogen C-Alkylation of Oxindoles with Alcohols.

A general and efficient iron‐catalyzed C‐alkylation of oxindoles has been developed. This borrowing hydrogen approach employing a (cyclopentadienone)iron carbonyl complex (2 mol %) exhibited a broad reaction scope, allowing benzylic and simple primary and secondary aliphatic alcohols to be employed as alkylating agents. A variety of oxindoles underwent selective mono‐C3‐alkylation in good‐to‐excellent isolated yields (28 examples, 50–92 % yield, 79 % average yield).

Manganese-Catalyzed N-Alkylation of Sulfonamides Using Alcohols.

An efficient manganese-catalyzed N-alkylation of sulfonamides has been developed. This borrowing hydrogen approach employs a well-defined and bench-stable Mn(I) PNP pincer precatalyst, allowing benzylic and simple primary aliphatic alcohols to be employed as alkylating agents. A diverse range of aryl and alkyl sulfonamides undergoes mono- N-alkylation in excellent isolated yields (32 examples, 85% average yield).

Assembly of Diversely Substituted Quinolines via Aerobic Oxidative Aromatization from Simple Alcohols and Anilines.

An aerobic oxidative aromatization of simple aliphatic alcohols and anilines under the Pd(OAc)2/2,4,6-Collidine/Brønsted acid catalytic system has been established, providing a direct approach for the preparation of diverse substituted quinoline derivatives in high yields with wide functional group tolerance. Practically, the protocol can be easily scaled up to gram-scale and was utilized in the concise formal synthesis of a promising herbicide candidate.

ChemInform Abstract: Tandem α‐Alkylation/Asymmetric Transfer Hydrogenation of Acetophenones with Primary Alcohols.

AbstractAn interesting direct α‐alkylation/asymmetric transfer hydrogenation of acetophenones is achieved with simple primary aliphatic alcohols using an in situ generated Ru‐catalyst having an amino acid hydroxy amide ligand.

The synthesis of bisphosphonate analogues of nucleotides – derivatives of (α-phenyl)(α-fluoro)methylenebisphosphonic acids

The synthetic methods of fluorine-containing mimetics of nucleozide-diphosphates based on the derivatives of (α-fluoro)(α-phenyl) methylenebisphosphonic acid containing the residues of 2-{1-[4-(toluene-4-sulfonyl)-5-per-fluoroalkyl-[1,2,3]triazol-2-yl]-ethoxy}-ethelene and {2,2-dimethyl-6-[4(toluene-4-sulfonyl)-5-pentafluoroethyl-[1,2,3] triazol-2-yl]-tetrahyro-furo[3,4-d][1,3]dioxol-4-yl}-methylene as ester groups have been developed. Selective mono-and bisdealkylation of methoxy-groups in the tetramethyl ester of (α-fluoro)(α-phenyl)methylenebisphosphonic acid allows to prepare in high yields the corresponding trimethyl or symmetrical dimethyl esters containing one or two free reactive phosphonic acids groups. These compounds are convenient starting materials for the synthesis of mixed esters of (α-fluoro)(α-phenyl)methylenebisphosphonic acid by esterefication of acidic functionalities using simple aliphatic alcohols (n-butanol) and such analogues of nucleosides as 2-{1-[4-(toluene-4-sulfonyl)-5-perfluoroalkyl-[1,2,3]triazol-2-yl]-ethoxy}-ethanols and {2,2-dimethyl-6-[4(toluene-4-sulfonyl)-5-pentafluoroethyl-[1,2,3]triazol-2-yl]-tetrahyro-furo[3,4-d][1,3]dioxol-4-yl}-methanol. The structure of the compounds obtained has been proven using the methods of IR, NMR (1H, 13C, 19F, 31P) spectroscopy, mass-spectra, and elemental analysis. The cytotoxicity and antiviral activity of the compounds synthesized have been studied on the model of the Epstein-Barr virus. The compound possessing a significant inhibitory effect on the Epstein-Barr virus reproduction has been found.

ChemInform Abstract: Iron‐Catalyzed One‐Pot 2,3‐Diarylquinazolinone Formation from 2‐Nitrobenzamides and Alcohols.

AbstractThis method is suitable for benzylic alcohol derivatives (II), but not for simple aliphatic alcohols (e.

Remarkable effect of simple aliphatic alcohols on the controlled aerobic oxidation of toluene catalyzed by (T(p-Cl)PP)MnF/NHPI

The remarkable effect of simple aliphatic alcohols on the controlled oxidation of toluene with molecular oxygen over [5,10,15,20-tetrakis(p-chlorophenyl)porphinato]manganese fluoride (T(p-Cl)PPMnF) and N-hydroxyphthalimide (NHPI) was reported. The influences of reaction conditions such as the concentration and structure of alcohols, temperature and catalyst concentration on the promotion effect were also studied. UV–vis spectra were used to investigate the possible structure of reaction intermediate derived from the catalyst (T(p-Cl)PP)MnF in the toluene oxidation systems in the presence of methanol. The results showed that the added methanol interacted with catalyst (T(p-Cl)PP)MnF to form the coordination compound [(T(p-Cl)PP)MnIII(ROH)2]+, which subsequently was transformed into a high valent manganese-oxo radical cation intermediate [(T(p-Cl)PP)MnIV(O)(CH3OH)]+ in the oxidation systems. We deduce that the formation of [(T(p-Cl)PP)MnIV(O)(CH3OH)]+ and its higher reactivity toward toluene may be responsible for the better results observed. On the basis of the results obtained, a possible mechanism of the controlled oxidation of toluene with dioxygen over (T(p-Cl)PP)MnF/NHPI in the presence of the aliphatic alcohols was proposed.

Effect of simple aliphatic alcohol thin films on the laser induced excimer fluorescence decay of naphthalene on \alpha-alumina during temperature programmed desorption

The effect of a homologous series of simple aliphatic alcohols on the laser induced fluorescence decay of naphthalene that had been vapor deposited on a crystal of α-alumina during temperature programmed desorption was observed. At temperatures before the desorption of the alcohol, thermally induced percolation caused the formation of molecular naphthalene possibly due to solvation. Concurrently, a relatively unstable excimer species was observed that had a much

Sulfonato–Cu(salen) Complex CatalyzedN‐Arylation of Aliphatic Amines with Aryl Halides in Water

AbstractA water‐soluble sulfonato‐Cu(salen) complex catalyzed procedure for theN‐arylation of simple aliphatic amines, amino alcohols and amino acids in pure water have been developed. A variety of substituted aryl iodides, bromides and electron‐deficient chlorides were found to be applicable, and 1,2‐disubstituted benzimidazoles could be prepared easily by a cascade amination/condensation process in this catalytic system.

ChemInform Abstract: Synthesis of Imines from Nitrobenzene and TiO2 Particles Suspended in Alcohols via Semiconductor Photocatalysis Type B.

AbstractLow power black light photolysis of a solution of nitrobenzene in simple aliphatic alcohols in the presence of suspended titanium dioxide results in formation of small amounts of imines and for longer aliphatic chains together with aniline as direct reduction product.

The absolute configuration of simple aliphatic alcohols through a chemical/computational approach: triarylether derivatives of (+)- endo-2-norborneol as a case study

The reliable determination of the absolute configuration of (+)- endo-2-norborneol 1, chosen as a representative case of simple aliphatic UV–vis transparent alcohols, was obtained by transforming this compound in its 1-naphthyl-diphenylmethyl ether 5 whose ECD spectrum displays several, low-lying, intense Cotton effects, which can be satisfactorily simulated in position, sign, and intensity by TDDFT/B3LYP/6-31G ∗ calculations. This result represents a possible, general, new approach to the absolute configuration of aliphatic alcohols.

Poly(malachite green) at nafion doped multi-walled carbon nanotube composite film for simple aliphatic alcohols sensor

Conductive composite film which contains nafion (NF) doped multi-walled carbon nanotubes (MWCNTs) along with the incorporation of poly(malachite green) (PMG) has been synthesized on glassy carbon electrode (GCE), gold and indium tin oxide (ITO) electrodes by potentiostatic methods. The presence of MWCNTs in the composite film (MWCNTs–NF–PMG) enhances surface coverage concentration ( Γ) of PMG to ≈396%, and increases the electron transfer rate constant ( k s) to ≈305%. Similarly, electrochemical quartz crystal microbalance study reveals the enhancement in the deposition of PMG at MWCNTs-NF film. The surface morphology of the composite film deposited on ITO electrode has been studied using scanning electron microscopy (SEM) and scanning tunneling microscopy (STM). These two techniques reveal that the PMG incorporated on MWCNTs–NF film. The MWCNTs–NF–PMG composite film also exhibits promising enhanced electrocatalytic activity towards the simple aliphatic alcohols such as methanol, ethanol and propanol. The electroanalytical responses of analytes at NF–PMG and MWCNTs–NF–PMG films were measured using both cyclic voltammetry (CV) and differential pulse voltammetry (DPV). From electroanalytical studies, well defined voltammetric peaks have been obtained at MWCNTs–NF–PMG composite film for methanol, ethanol and propanol at Epa = 609, 614 and 602 mV respectively. The sensitivity of MWCNTs–NF–PMG composite film towards methanol, ethanol and propanol in CV technique are 0.59, 0.36 and 0.92 μA mM −1 cm −2 respectively, which are higher than NF–PMG film. Further, the sensitivity values obtained using DPV are higher than the values obtained using CV technique.

Phosphotungstic Acid Catalyzed Amidation of Alcohols

AbstractMild nucleophilic substitution reactions of benzhydrylic, benzylic, allylic, and simple aliphatic alcohols with sulfonamides, benzamide, and 4‐nitroaniline in the presence of 12‐phosphotungstic acid as an efficient, eco‐friendly, cheap, and air‐ and moisture‐tolerant catalyst for the construction of C–N bonds has been investigated. The amine derivatives were obtained in good yields (up to 98 %). The reusable nature of the 12‐phosphotungstic acid makes this protocol more attractive.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

Facile synthesis of simple mono-alkyl phosphates from phosphoric acid and alcohols

Simple aliphatic alcohols can be selectively converted into mono-alkyl phosphate esters at the laboratory scale using the acetic anhydride-mediated activation of inorganic phosphate.

Water and alcohol(s): what's the difference? A proton NMR and DFT study of hetero‐association with pyridine

AbstractHetero‐association of water and some simple aliphatic alcohols with pyridine in benzene has been studied by 1H nuclear magnetic resonance (NMR) spectroscopy at very low donor concentration, where self‐association is negligible. Association constants for the formation of 1:1 and 2:1 pyridine:water complexes can then be determined without recourse to ad hoc computer programmes. That for association of a second pyridine with water is about 10 times lower than for the first. Reaction parameters for the first association with water are very similar to those for the alcohols, whereas the reaction enthalpy for the second association is somewhat smaller. The chemical shift of the OH protons and the HCOH coupling constants for alcohols at high dilution in benzene are almost identical with gas‐phase data. The change in chemical shift upon association with pyridine correlates with the free energy of the reaction. Quantum mechanical calculations [BPE0 functional, 6‐311+G(d,p) basis set and a polarized continuum model of the solvent (IEFPCM)] have been run on complexes of pyridine with water, both 1:1 and 2:1, and with four alcohols. Calculated reaction enthalpies are in qualitative and, in some cases, almost quantitative agreement with the experimental data. The association constants for 1:1 complexation of pyridine with alcohols follow a rough Taft correlation in terms of polar substituent constants. Substituent size, even in the case of very bulky groups, seems to be unimportant. Copyright © 2008 John Wiley & Sons, Ltd.

単純アルコールを活用する炭素‐炭素結合形成反応

This mini review describes recent advances in transition metal-catalyzed carbon-carbon bond-forming reactions that allow direct use of simple aliphatic alcohols without derivatization or pre-activation. The sp3 carbon-oxygen bonds of alcohols can be transformed to carbon-carbon bonds through one-pot multiple reactions containing redox processes.