Novel synthesis of tertiary alkyl,secondary and tertiary benzyl,and allyl selenides from the corresponding alcohols

We report an efficient synthesis of the title compounds from alcohols and selenols. The scope and limitations of the new method are disclosed.     

Ruthenium-catalysed synthesis of tertiary amines from alcohols

Secondary amines have been converted into tertiary amines by reactions with primary alcohols. A catalytic system of [Ru(cymene)Cl₂]₂ with dppf has been shown to be effective for this transformation for a range of primary alcohols and secondary amines. The methodology has been applied to the one pot synthesis of Piribedil and other piperazine and morpholine-containing products.     

Ni-catalysed, domino synthesis of tertiary alcohols from secondary alcohols

The use of in situ generated (NHC)-Ni catalytic species (NHC = N-heterocyclic carbene) allows for the synthesis, in short reaction times, of a variety of tertiary alcohols from secondary alcohols through a domino oxidation-addition protocol.     

Preparative synthesis of primary and secondary alkyl chlorides from alcohols

Conclusions We have developed a preparative single-stage tosylate method for obtaining chlorides from secondary and primary alcohols which isomerize when chlorinated by other methods.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2506–2508, November, 1987.     

Asymmetric synthesis of tertiary benzylic alcohols

Vinyl, aryl, and alkynyl organometallics add to ketones containing a stereogenic sulfoxide. Tertiary alcohols are generated in diastereomerically and enantiomerically pure form. Reductive lithiation converts the sulfoxide into a variety of useful functional groups.     

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.     

Facile solid-phase synthesis of biotinylated alkyl thiols

Biotinylated alkyl thiols with the capacity to graft avidin proteins are in increasing demand for the development of self-assembled monolayers on gold. Here we propose 2-Chlorotrityl Chloride solid-phase resin as a new platform to produce these functionalized alkyl thiols. Biotinylated alkyl thiols of non-obvious solution synthesis were obtained rapidly using this method and without previous purification steps.     

Ruthenium catalyzed synthesis of secondary or tertiary amines from amines and alcohols

Unsymmetrical secondary and tertiary amines are prepared by the ruthenium catalyzed reaction of alcohols with amines, which provides highly efficient method for synthesis of cyclic amines.     

Stereospecific synthesis of some tertiary homoallyl monoterpene alcohols

Conclusions Metallation of 2,2-dimethylcyclopropyl bromide and subsequent reaction with C₅ aldehydes yielded the corresponding C₁₀ cyclopropylcarbinols whose acid-catalyzed rearrangement gave trans-homoallyl tertiary monoterpene alcohols with high regio- and stereospecificity.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2545–2548, November, 1982.     

Improved synthesis of tertiary propargyl alcohols by the Favorskii reaction of alkyl aryl (hetaryl) ketones with acetylene

Alkyl aryl (hetaryl) ketones react with acetylene under atmospheric pressure in the superbasic system KOH-EtOH-H₂O-DMSO at 10–15°C (2 h) to give the corresponding tertiary propargyl alcohols in up to 91% yield. The procedure requires no large excess of KOH and low-boiling inflammable solvents, produces few wastes, and is safe and convenient on the laboratory scale; there are no limitations for its large-scale application.     

Facile synthesis of aliphatic isothiocyanates and thioureas on solid phase using peptide coupling reagents

Peptide coupling reagents can be used as versatile reagents for the formation of aliphatic isothiocyanates and thioureas on solid phase from the corresponding solid-phase anchored aliphatic primary amines. The formation of the thioureas is fast and highly chemoselective, and proceeds via formation of the intermediate isothiocyanate. The isothiocyanate and subsequent thiourea formation take place under standard peptide coupling conditions using carbon disulfide as the ‘amino acid’. The thioureas are released from the resin and isolated in moderate to high yields.     

One-pot synthesis of secondary or tertiary amines from alcohols and amines via alkoxyphosphonium salts

Secondary or tertiary amines may be prepared from primary alcohols and primary or secondary amines by treating triphenylphosphine with N-bromosuccinimide (NBS) in the presence of the alcohol at low temperature, followed by addition of the amine and heating for about 1 h. The yield of amine is good to fair, decreasing sharply with sterically congested alcohols and starting amines.     

Simple synthesis of fresh alkyl iodides using alcohols and hydriodic acid

A simple synthesis of fresh alkyl iodides using alcohols and hydriodic acid (HI) is reported. The alkyl iodides were obtained in quick and easy work-up with good to excellent yields (66-94%) and very high purities (97-99%). Freshly prepared iodomethane and 1-iodobutane were applied to synthesize biologically relevant 3,7-dimethyladenine and 9-butyladenine, which were characterized thoroughly using 1D and 2D NMR, individually.     

Facile protocol for the highly regioselective and stereodivergent synthesis of substituted bishomoallylic alcohols from esters

Regio- and diastereoselective preparation of bishomoallylic alcohols was realized by a facile four-step protocol including alpha,alpha'-selective zinc-mediated bispropargylation of unactivated esters and stereoselective reduction of the resulting bishomopropargylic alcohols.     

Facile synthesis of 1-aminoisoquinolines via the tandem reactions of 2-alkynylbenzaldoximes with isothiocyanates

A new, concise, and efficient route for the synthesis of 1-aminoisoquinolines in good to excellent yields is described; this involves the reaction of 2-alkynylbenzaldoximes and isothiocyanates, which is catalyzed by silver triflate in dichloromethane, at room temperature. This transformation involves tandem 6-endo cyclization, [3+2] cycloaddition, and subsequent rearrangement. The simple operational protocol provides a cost-effective, diversity-oriented route to 1-aminoisoquinolines under neutral, mild conditions.     

Improved synthesis of tertiary alcohols from reactions of organoboranes with 2-lithio-1,3-benzodithioles

Treatment of trialkylboranes with 2-lithio-1,3-benzodithioles and then mercuric chloride (or methyl fluorosulhonate) followed by oxidation gives tertiary alcohols in high yields. The method is applicable to reactions of hindered organoboranes that fail using 1-lithio-1,1-bis(phenylthio)alkanes.     

The synthesis of organosilicon diacetylene alcohols with conjugate tertiary bonds

Summary A method was developed for obtaining organosilicon diacetylene alcohols with conjugate tertiary bonds.