Cyclic Allylic Alcohols Research Articles

Regiospecific access to cyclic allylic alcohols by reductive alkylation of α-alkyloxy-epoxides

Allylic alcohols are synthesized by treatment of α-alkyloxy-epoxides with organolithium reagents; The reaction proceeds via a carbenoid pathway.

Hydroxyselenation of allylic alcohols

Hydroxyselenation of terminal or cyclic allylic alcohols occurs with high regio- and stereoselectivity to give β,β′-dihydroxyphenylselenated adducts in high yields. A mechanism for this selectivity is proposed. The utility of these adducts is illustrated by the conversion of the hydroxyselenide ( 9a) to the epoxide ( 11) via the intermediacy of a selenone.

Chiral poisoning in the kinetic resolution of allylic alcohols

Recently, hydrogenations of allylic alcohols using ruthenium catalysts with enantiomerically pure phosphines, such as ( R)-BINAP were reported to be useful for the kinetic resolution of cyclic allylic alcohols. These kinetic resolutions can also be effected using racemic BINAP and preferentially deactivating one enantiomer of the catalyst with an enantiomerically pure chiral poison. Poisoning of racemic (BINAP)-RuCl 2 (dmf) x with (1 R,2 S)-ephedrine provided ( R)-2-cyclohexenol in 93% ee at 72% conversion.

ChemInform Abstract: Substrate Modification to Increase the Enantioselectivity of Hydrolases. A Route to Optically‐Active Cyclic Allylic Alcohols.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Substrate modification to increase the enantioselectivity of hydrolases. A route to optically-active cyclic allylic alcohols.

The esterase-catalyzed resolution of the cyclic allylic acetates-1-acetyloxy-2-cyclopentene, 1-acetyloxy-2-cyclohexene, and 1-acetyloxy-2-cycloheptene - was not enantioseleclive. We hypothesized that this inefficiency stems from the similarity in size of the substituents at the stereocenter (CH 2CH 2 vs. CHCH). To increase the enantioselectivity, we resolved precursors to these cyclic allylic alcohols: esters of trans-2-bromocycloalkanols (C 5, C 6, C 7). These esters had a larger difference in the size of the substituents (CH 2 vs. CHBr) at the stereocenter and were efficiently resolved by both cholesterol esterase and lipase from Pseudomonas cepacia (Amano P, PCL). A synthetic-scale resolution with PCL yielded the (1S,2S)-1-butanoyloxy-2-bromocycloalkanes in >98% ee. Heating with DBU to eliminate HBr, followed by reduction with LiAlH 4 to cleave the ester, yielded the allylic alcohols: (S)-(−)-2-cyclopenten-1-ol (65% ee), (S)-(−)-2-cyclohexen-1-ol (>99% ee), and (S)-(−)-2-cyclohepten-1-ol (>98% ee).

Tandem Double Michael Addition/Sigmatropic Rearrangements for the Construction of Highly Substituted Rings: A Synthesis of the Taxol A Ring

A new ring synthesis is described which relies on a double Michael addition of enolates derived from α,β-unsaturated ketones to allenyl sulphoxides. The resulting allylic sulphoxides can be isolated or rearranged in situ to cyclic allylic alcohols.

A simple one-step synthesis of alkylation product from cyclic allylic alcohol and resorcinol

The alkylation of resorcinol with cyclic allylic alcohol in non-aqueous acid medium gives intermolecular Friedel-Craft compounds. The products are primary alkylation products. The linkage always occurs between carbon 3 of cyclic allylic alcohol and the position 2, 4, 5 or 6 of the resorcinol.

Boron trifluoride Etherate-Catalyzed formation of resorcinols: Synthesis of 3,4,5,6-Tetrahydro-7-hydroxy-2 methyl-9-alkyl-2,6-methano-2H-1-benzoxocins

3,4,5,6-Tetrahydro-7-hydroxy-2-methyl-9-alkyl-2,6-methano-2H-1-benzoxocins are readily prepared by boron trifluoride etherate-catalyzed cyclization of resorcinols with cyclic allylic alcohol.

ChemInform Abstract: Synthesis of Unsaturated Bicyclic Lactones and Acetals via Palladium‐Promoted Cyclization of Cyclic Allylic Alcohols.

AbstractThe mercurioacetates (I), (IV), or (VIII), derived from cyclic allyl ethers, are treated with palladium(II) chloride and lithium chloride in the presence of triethylamine to produce mixtures of valence‐tautomeric fused γ‐lactones.

Stereoselective synthesis of (-)-(5R,6S)-6-acetoxy-5-hexadecanolide, the mosquito oviposition attractant pheromone

The natural mosquito oviposition attractant pheromone,(-)-(5R,6S)- 6-acetoxy-5-hexadecanolide ( 1 ) was synthesized from readily available 1,2-cyclohexanediol, using kinetic resolution of cyclic allylic alcohol by modified Sharpless asymmetric epoxidation reagent as the key step.

Synthesis of unsaturated bicyclic lactones and acetals via palladium-promoted cyclization of cyclic allylic alcohols

Unsaturated bicyclic lactones are readily prepared by converting cyclic allylic alcohols to the corresponding α-chloromercurio acetate esters and reacting them with Li 2PdCl 4. The corresponding acetals can be synthesized directly by reaction of the allylic alcohols with ethyl vinyl ether and Pd(OAc) 2.

Synthetic applications of radical ring-opening: use of cyclopropylmethyl radicals

Cyclopropanation of cyclic allylic alcohols followed by radical deoxygenation leads, by peripheral ring-opening of the cyclopropylmethyl system, to alkyl-substituted cycloalkenes (Scheme 1); the alkyl group can itself be substituted (during the cyclopropanation stage), synthetic equivalents of allylic alcohols can be used, and the overall process occurs with predictable stereo- and regio-chemistry.

Configurationally dependent hydroxyl group effects on 13C nuclear magnetic resonance chemical shifts of olefinic carbons in cyclic six-membered allylic alcohols

The differences in chemical shifts of olefinic carbons, Δδ(sp2), of pseudoequatorial and pseudoaxial six-membered allylic alcohols were correlated with the Δδ(sp2) values of their parent olefins. The results obtained reflect configurationally dependent substituent effects, the magnitude of which could be used for the stereochemical assignment of the hydroxyl group in these compounds.

ChemInform Abstract: Synthesis of Diacids and Keto Acids by Ruthenium Tetraoxide Catalyzed Oxidation of Cyclic Allylic Alcohols and α,β‐Unsaturated Ketones.

AbstractOxidative cleavage of the cyclic alcohols (I), (III), or (V) gives either the keto acids (II) and (VI) or the diacid (IV).

Preparation of chiral allylic alcohols using Rhizopusnigricans. Use of the Harada–Nakanishi exciton chirality method for verifying configurational assignments of allylic alcohols

A series of (R) acyclic and cyclic allylic alcohols was prepared by enantioselective hydrolysis of acetates using Rhizopusnigricans. The configurations of the alcohols formed were established by chemical methods and, in the case of 1,2-benzocyclohepta-1,3-dien-5-yl camphanate, by X-ray crystallography. In conjunction with the Harada–Nakanishi rule, the chiroptical properties of the p-bromobenzoate esters were used to verify configurations tentatively assigned from their method of preparation.

Synthesis of diacids and keto-acids by ruthenium tetraoxide-catalyzed oxidation of cyclic allylic alcohols and .alpha.,.beta.-unsaturated ketones

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis of diacids and keto-acids by ruthenium tetraoxide-catalyzed oxidation of cyclic allylic alcohols and .alpha.,.beta.-unsaturated ketonesFrancis X. Webster, Jose Rivas-Enterrios, and Robert M. SilversteinCite this: J. Org. Chem. 1987, 52, 4, 689–691Publication Date (Print):February 1, 1987Publication History Published online1 May 2002Published inissue 1 February 1987https://doi.org/10.1021/jo00380a040RIGHTS & PERMISSIONSArticle Views705Altmetric-Citations54LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (388 KB) Get e-Alerts Get e-Alerts

Configurational assignment of epimeric secondary six-membered allylic alcohols by 13C nuclear magnetic resonance spectroscopy. A new approach

On the basis of the effects of the hydroxyl group on the 13C nuclear magnetic resonance chemical shifts of the olefinic carbons, a new parameter was defined and a new rule was proposed for the assignment of the stereochemistry of secondary six-membered cyclic allylic alcohols.

Hydrogen transfer reaction of allylic alcohols catalyzed by a molybdenum complex

Abstract Allylic alcohols undergo hydrogen transfer reactions in the presence of a catalytic amount of the dinitrogen complex trans-Mo(N2)2(dppe)2 (dppe = Ph2PCH2-CH2PPh2). From the acyclic allylic alcohols, saturated carbonyl compounds were obtained as the main products whereas from the cyclic allylic alcohols, unsaturated ketones and saturated alcohols were formed predominantly. Accompanying the hydrogen transfer reaction, a decarbonylation reaction occurred simultaneously to give a molybdenum carbonyl complex, cis-Mo(CO)2(dppe)2 as well as the hydrocarbon in certain cases. The mechanisms of both reactions are discussed.

N-π Interaction between an oxygen lone pair and π-electrons in cyclic allylic alcohols and ethers; carbon-13 nuclear magnetic resonance spectra, catalytic hydrogenation, and CNDO/2 calculations

In order to elucidate the n-π interaction between an oxygen lone pair and π-electrons, 13C n.m.r. spectra have been obtained for several cyclic allylic alcohols and ethers. The chemical shifts for sp2-carbons of these compounds are compared with those of the corresponding hydrocarbons. The chemical shift differences (Δδ) between compounds in which the oxygen atoms are placed at an anticlinal position with respect to the double bond and the corresponding hydrocarbons are different from those of a set of compounds, the oxygens of which are synperiplanar. We have also studied catalytic hydrogenation of and CNDO/2 calculations for these cyclic allylic compounds. These results are discussed in terms of homoconjugation

Vanadium-catalyzed epoxidation of cyclic allylic alcohols. Stereoselectivity and stereocontrol mechanism

Vanadium-catalyzed epoxidation of cyclic allylic alcohols. Stereoselectivity and stereocontrol mechanism