Superparamagnetic iron oxide as an efficient and recoverable catalyst for rapid and selective trimethylsilyl protection of hydroxyl groups

At room temperature and under solvent‐free conditions, various types of alcohols and phenols were efficiently protected within a few minutes using hexamethyldisilazane and magnetically recoverable Fe₃O₄. Preferential protection of primary alcohols was observed when they competed with secondary or tertiary alcohols. Highly selective protection of phenols in the presence of aromatic amines or thiophenol was also observed. Copyright © 2008 John Wiley & Sons, Ltd.     

Facile tert‐Butoxycarbonylation of Alcohols,Phenols, and Amines using BiCl3 as a Mild and Efficient Catalyst

Facile tert‐butoxycarbonylation of alcohols, phenols, and amines is described by treatment of alcohols, phenols, and amines with di‐tert‐butyl dicarbonate in the presence of a catalytic amount of bismuth(III) chloride, a mild and efficient catalyst, at room temperature in excellent yields.     

N,N ′-Diiodo-N,N′-1,2-ethanediylbis(p-toluenesulfonamide) as an Efficient Catalyst for Acetylation of Alcohols,Phenols, Amines,and Thiols Under Solvent-Free Conditions

N,N′-Diiodo-N,N′-1,2-ethanediylbis(p-toluenesulfonamide) (NIBTS) is a highly efficient catalyst for the acetylation of alcohols, phenols, amines, and thiols under solvent-free conditions. Primary, secondary, tertiary alcohols; phenols; amines; and thiols can be easily acetylated in good to excellent yields at 80 °C.     

Rice husk: Introduction of a green,cheap and reusable catalyst for the protection of alcohols,phenols, amines and thiols

A mild, efficient and eco-friendly protocol for the chemoselective protection of benzylic and primary and less hindered secondary aliphatic alcohols and phenols as trimethylsilyl ethers and different types of amines as N-tert-butylcarbamates is developed using rice husk (RiH) as the catalyst. This reagent is also able to catalyze the acetylation of alcohols, phenols, thiols and amines with acetic anhydride. Easy work-up, relatively short reaction times, excellent yields and low cost, availability and reusability of the catalyst are the striking features of this methodology, which can be considered to be one of the best and general methods for the protection of alcohols, phenols, thiols and amines. In addition, the use of a green reagent in the above-mentioned reactions results in a reduction of environmental pollution and of the cost of the applied methods.     

Reactions on a solid surface. A simple, economical, and efficient acylation of alcohols and amines over Al2O3

Al(2)O(3) brings about a rapid acylation of a range of alcohols and amines with acid chlorides and acid anhydrides, respectively. Amines are easily Boc- and Cbz-protected on reaction with Boc-anhydride and Cbz-Cl, respectively. The acylation of phenols is slow enough to allow chemoselective acylation of alcohols and amines in the presence of phenols.     

N- and O-arylation with triphenylantimony ortho-phenylenedioxides

2,2,2-Triphenyl-1,3,2-benzodioxastibolanes react with alcohols, phenols, and amines in the presence of copper salts to give the corresponding O- and N-phenyl derivatives. Cyclic Sb^V dialkoxide containing an electron-withdrawing nitro group in the dioxastibolane fragment is most reactive in N-phenylation of primary and secondary amines. Organoantimony analogs containing electron-donating groups are more efficient in O-phenylation of primary and secondary alcohols and phenols.     

Zinc oxide (ZnO) as a new, highly efficient, and reusable catalyst for acylation of alcohols, phenols and amines under solvent free conditions

Zinc oxide (ZnO) is a highly efficient catalyst for the acylation of a variety of alcohols, phenols and amines with acid chlorides or acid anhydrides under solvent free conditions. Primary, secondary, tertiary, allylic and benzylic alcohols, diols and phenols with electron donating or withdrawing substituents can be easily acylated in good to excellent yield.     

Electrostatic catalysis by ionic aggregates: scope and limitations of Mg(ClO4)2 as acylation catalyst

Alkali and alkaline earth metal perchlorates exhibit electrostatic catalysis in the activation of anhydrides for the acylation reaction. Perchlorates with higher values of the charge-size function of the metal ion exhibit better catalytic activity following the order Mg(ClO₄)₂>Ba(ClO₄)₂>LiClO₄. Acylation of structurally diverse phenols, thiols, alcohols, and amines have been carried out with stoichiometric amounts of anhydride at room temperature under solvent free conditions in the presence of catalytic amount of Mg(ClO₄)₂. Sterically hindered and electron deficient phenols are efficiently acylated. Acylation with sterically hindered anhydrides such as iso-butyric, pivalic, and benzoic anhydrides are carried out with phenols and alcohols in excellent yields. Acid-sensitive alcohols are acylated in excellent yields without any competitive side reactions.     

Zirconyl triflate: A new, highly efficient and reusable catalyst for acetylation and benzoylation of alcohols, phenols, amines and thiols with acetic and benzoic anhydrides

Highly efficient acetylation and benzoylation of alcohols, phenols, amines and thiols with acetic and benzoic anhydrides catalyzed by new and reusable zirconyl triflate, ZrO(OTf)₂, is reported. The high catalytic activity of electron deficient ZrO(OTf)₂ can be used for the acetylation and benzoylation of not only primary alcohols but also sterically-hindered secondary and tertiary alcohols with acetic and benzoic anhydrides. Acetylation of phenols with acetic and benzoic anhydrides was achieved to afford the desired acetates and benzoates efficiently. This catalyst also efficiently catalyzed the acetylation and benzoylation of amines and thiols whereby the corresponding amides and thioesters were obtained in good to excellent yields. This catalyst can be reused several times without loss of its activity.     

NMR spectral studies—XII : Trichloroacetyl isocyanate as an in situ derivatizing reagent for C NMR spectroscopy of alcohols, phenols and amines

Trichloroacetyl isocyanate (TAI) has been found to be a useful in situ derivatizing reagent for the ¹³C NMR studies on alcohols, phenols and amines. The carbinol carbon of aliphatic alcohols shows downfield shifts the size of which permits distinction between primary, secondary and tertiary saturated alcohols. In allylic and propargylic alcohols the γ-carbon undergoes large downfield shifts while the β-carbon is shifted upfield. In the case of phenols, the OH-bearing carbon is shifted upfield, the o - and p-carbons are shifted downfield but m-carbons are virtually unaffected. Addition of TAI to amines and anilines produces various size shifts for the - and β-carbons. The use of TAI is thus a valuable aid in the assignment of the resonance signal of a carbon carrying an OH or NH-group as well as some neighboring carbons in ¹³C NMR spectra for structural and biosynthetic studies.     

4- Hydroxy-3, 5-di-tert -butylbenzalchloride in the synthesis of sterically hindered phenols

Conclusions We have obtained 4-hydroxy-3,5-di-tert-butylbenzalchloride by reacting 4-hydroxy-3, 5-di-tert-butylbenzaldehyde with thionyl chloride, and have studied its reactions with alcohols, phenols, and amines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 902–904, April, 1968.     

V（HSO4）3 catalyzed chemoselectivity acetylation of alcohols and phenols in solution and under solvent-free conditions

A variety of alcohols and phenols are efficiently acetylated with acetic anhydride in the presence of a catalytic amount of V(HSO4)3 in solution and under solvent free conditions.Mild reaction conditions,high yields of the products,easy procedure and selective acetylation of alcohols and phenols in the presence of amines and thiols are the main advantages of this procedure.     

MgBr2·OEt2 mediated protection of alcohols with hexamethyldisilazane: An efficient catalytic route for the preparation of silyl ethers under solvent-free conditions

Various types of alcohols and phenols were rapidly protected by hexamethyldisilazane in good to excellent yields at room temperature in the presence of catalytic amount of magnesium bromide ethyl etherate under solvent-free conditions. Good to excellent chemoselectivity was demonstrated for competitive protection of primary hydroxyls in the presence of secondary and tertiary alcohols. Highly selective protection of phenols in the presence of aromatic amines was also demonstrated successfully.     

Additive-Free Chemoselective Acylation of Amines and Thiols

Summary. Amines with different stereoelectronic nature were efficiently acylated at room temperature using acetic anhydride in the presence of no solvent or additive. Various thiols also react equally well under the same conditions. Chemoselective protection of amines in the presence of thiols, alcohols, and phenols and of thiols in the presence of alcohols, and phenols were achieved using competitive experiments.     

Heterocyclic nitro compounds

Reaction of 1-methyl-3,5-dinitro-1,2,4-triazole with alcohols or phenols in the presence of bases (tertiary amines) leads to replacement of the nitro group in the 5-position by an alkoxy or phenoxy group.For part IV, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 5, pp. 702–704, May, 1970.     

Deprotection by electrolysis: Part I. The application of homogeneous redox catalysis to the study of the reduction of tosyl esters and amides

The mechanism of the cathodic cleavage of tosylate protecting groups from alcohols, amines and phenols in dimethylformamide has been probed using the technique of homogeneous redox catalysis. Some nine tosyl esters and six tosyl amides have been investigated and it is confirmed that these deprotection reactions occur by cleavage of the anion radicals. The formal electrode potentials for the couples, neutral molecule/anion radical, are reported and it is shown that the rate constants for the cleavage of the anion radicals lie in the range 10⁴ s^?1 to >10⁸ s^?1. Indeed for aromatic amines and phenols, the homogeneous charge transfer between the catalyst and the substrate becomes the rate determining step.     

Fluoroboric acid adsorbed on silica gel as a new and efficient catalyst for acylation of phenols, thiols, alcohols, and amines

Fluoroboric acid supported on silica gel efficiently catalyzes acylation of structurally diverse phenols, alcohols, thiols, and amines under solvent free conditions. Acid-sensitive alcohols are smoothly acylated without competitive side reactions.     

Palladium-catalyzed carbonylation of aryl triplates. Synthesis of arenecarboxylic acid derivatives from phenols

Various aryl triflates derived from phenols were converted into aryl esters or amides in good yields by a palladium-catalyzed reaction with carbon monoxide and alcohols or amines.     

Palladium(II) chloride catalyzed selective acetylation of alcohols with vinyl acetate

PdCl(2) can catalyze the acetylation of primary and secondary alcohols with vinyl acetate. The reaction is selective and mild with high yields. Tertiary alcohols, phenols and amines are unaffected under these reaction conditions.     

Rice Husk Ash: A New,Cheap, Efficient,and Reusable Reagent for the Protection of Alcohols,Phenols, Amines,and Thiols

Abstract

A mild, efficient, and eco-friendly protocol for the protection of alcohols and phenols as trimethylsilyl ethers has been developed using rice husk ash as a reagent. This reagent is also able to catalyze the acetylation of alcohols, phenols, thiols, and amines with acetic anhydride. All reactions were performed under mild conditions in good to high yields.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional text, tables, and figures.]