Prins Reaction Research Articles

Stereocontrolled derivatization of 3-methoxyestra-1,3,5(10), n-tetraenes via lewis acid promoted prins reactions, (n=7; 8(9))

Steroidal olefins 1 and 3 undergo dimethylaluminum chloride-mediated Prins reactions with paraformaldehyde to furnish homoallylic alcohols 4 and 16 as major products. These ene reaction-type intermediates are converted into 6 and 17 by hydroxyl group-assisted catalytic hydrogenation, while Birch reduction of 4 proceeds to the 8β-epimer 11. The saturated alcohols thus obtained serve as convenient precursors to methyl derivatives 10, 14, and 20.

Synthesis of (±)-2′,3′-didehydro-2′,3′-dideoxy nucleosides via a modified Prins reaction and palladium(0) catalysed coupling

Cyclopentenyl allylic acetates have been prepared in diastereoisomerically enriched form by modification of the Prins reaction. Palladium(0) catalysed coupling between these allylic acetates and a heteroaromatic base provides a highly convergent and direct route for synthesising carbocyclic 2′,3′-didehydro-2′,3′-dideoxy nucleosides. The method is exemplified by the coupling reaction with adenine which yields (±)-2′,3′-didehydro-2′,3′-dideoxyaristeromycin 5′-O-acetate 22 in 50% yield. This has been converted in two steps into (±)-aristeromycin triacetate 5.

Reactions of β-Pinene with Aromatic Aldehydes

Abstract Aromatic aldehydes add to β-pinene under Lewis acid catalyzed Prins reaction conditions and yield the corresponding homoallylic alcohols. The reactions proceed in poor yield when electron donating substituents are present on the aromatic ring.

ChemInform Abstract: Structural and Synthetic Studies in the 4‐Phenyl‐1,3‐dioxane Class. Part 1. Obtaining and Characterization of 5‐Chloro‐4‐phenyl‐1,3‐dioxanes by Prins Reactions.

AbstractPrins reaction of the β‐chlorostyrenes (I) with formaldehyde (II) in aqueous sulfuric acid leads to the formation of a mixture of the cis‐ and trans‐1,3‐dioxanes (IV) and (V) via the chlorophenylpropane‐1,3‐diols (III).

ChemInform Abstract: Allylic Hydroxymethylation of (.+‐.)‐2‐Oxabicyclo(3.3.0)oct‐7‐enone Under the Conditions of the Prins Reaction.

AbstractUnder the conditions of the Prins reaction the lactone (I) unexpectedly affords a mixture of the isomeric formates (III) and (IV), whose formation probably proceeds via an electrophilic allylic formylhydroxymethylation.

ChemInform Abstract: The Prins Reaction of Steroidal 4‐En‐3‐ones as a Means to the Extension of the Ring System of Steroids.

ChemInformVolume 20, Issue 23 Natural Products ChemInform Abstract: The Prins Reaction of Steroidal 4-En-3-ones as a Means to the Extension of the Ring System of Steroids. B. OSIPOWICZ, B. OSIPOWICZ Dep. Fundam. Chem., Agric. Univ., 50375 WroclawSearch for more papers by this author B. OSIPOWICZ, B. OSIPOWICZ Dep. Fundam. Chem., Agric. Univ., 50375 WroclawSearch for more papers by this author First published: June 6, 1989 https://doi.org/10.1002/chin.198923284Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume20, Issue23June 6, 1989 RelatedInformation

Stereoselective construction of the ring system of robustadials

The spiro[3,4-dihydro-2H-1-benzopyran-2,2′-bicyclo[3.1.1]heptane] framework of natural products Robustadials was constructed in a homochiral form. The synthesis started from 1 S -(−)-β-pinene, which was coupled to a substituted benzaldehyde using a Prins reaction, and incorporated a diastereoselective, Michael-type, intramolecular addition.

2-Carene in the Prins reaction

The Prins reaction of 2-carene with formaldehyde has been studied. The main reaction product is 2-hydroxymethyl-3-carene. The dehydration of 2-hydroxy-methyl-3-carene is accompanied by a skeletal rearrangement of the carane structure with the formation of products having a seven-membered ring.

ChemInform Abstract: Synthesis of Phytol Isomers: 7,11,15‐Trimethyl‐3‐methylenehexadecanol and 3,7,11,15‐Tetramethylhexadec‐3‐en‐1‐ol and Their Conversion into Vitamin E.

AbstractThe Prins reaction on norphytene (I) yields the diterpene alcohols (III) and (IV).

ChemInform Abstract: Prenylation of Camphene ‐ A Carbocationic Route to Isosantalene and Its Derivatives.

AbstractThe title compound (VIIIa) (isosantalene) is synthesized in an overall prenylation procedure from camphene (I) by known Prins reaction and conversion of the product (IV) to the target compound via the intermediates (V) and (VII).

ChemInform Abstract: The Formation of Isoprene by Means of a Vapor‐Phase Prins Reaction Between Formaldehyde and Isobutene.

ChemInform Abstract: The Formation of Isoprene by Means of a Vapor‐Phase Prins Reaction Between Formaldehyde and Isobutene.

The formation of isoprene by means of a vapor-phase prins reaction between formaldehyde and isobutene

The formation of isoprene by means of a vapor-phase prins reaction between formaldehyde and isobutene

Prenyaticn of camphene - a carbocationic route to isosantalene and its derivatives

Camphene 1 is converted Into 8-chloromethylcamphene 3 via Prins reaction. Treatment of 3 with zinc chloride/ether In the presence of isobutene gives the 1:1 adduct 11, from which isosantalene 7, its isomer 6, and the corresponding alcohol 5 are obtained.

Lewis Acid Induced Asymmetric Prins Reactions of Chiral Acetals with Alkenes

Abstract Me2AlCl induced reaction of acetal 1 with methylenecyclohexane at -78°C gives a 61% yield of 3 as a 7:3 mixture of diastereomers. MeAlCl2 induced reaction of acetal 2 with methylenecyclohexane gives a 53% yield of 6 as a 7:3 mixture of isomers. Reaction of 1 with isoprene gives 7 as a mixture of all 4 possible isomers. Reaction of acetal 8 with methylenecyclohexane gives the conjugate addition product 9 in 70% yield as a 4:1 mixture of isomers.

ChemInform Abstract: Chemistry of Di‐ and Tetrahydropyrans. Part 3. The Anomalous Behavior of 4‐Methyl‐5,6‐dihydropyran in the Prins Reaction.

AbstractDie Umsetzung des 4‐Methyl‐dihydropyrans (I) mit wäßrigem Formaldehyd (II) führt zu dem Dioxanderivat (III) und den Hydroxymethylverbindungen (IV) und (V).

Catalysis of the interphase reaction of ?-methylstyrene with formaldehyde by alkylbenzenesulfonic acids

1. Alkylbenzenesulfonic acids accelerate condensation of α-methylstyrene with formaldehyde (on conversion per acid group) significantly more strongly than sulfuric and oxalic acids. 2. The observed event is due to interphase transfer under conditions of acid catalysts (Prins reaction). Schemes which include transfer of the olefin to the aqueous phase and formaldehyde to the organic phase were proposed. The catalytic cycle includes the formation of an ion pair of the alkylbenzenesulfonic acid with formaldehyde due to the occurrence of the reaction in the organic phase.

ChemInform Abstract: Ketones in the Coupled Prins Reaction.

Chemischer InformationsdienstVolume 17, Issue 16 Heterocyclic Compounds ChemInform Abstract: Ketones in the Coupled Prins Reaction. U. G. IBATULLIN, U. G. IBATULLINSearch for more papers by this authorR. F. TALIPOV, R. F. TALIPOVSearch for more papers by this authorI. S. FAIZRAKHMANOV, I. S. FAIZRAKHMANOVSearch for more papers by this authorM. G. SAFAROV, M. G. SAFAROVSearch for more papers by this author U. G. IBATULLIN, U. G. IBATULLINSearch for more papers by this authorR. F. TALIPOV, R. F. TALIPOVSearch for more papers by this authorI. S. FAIZRAKHMANOV, I. S. FAIZRAKHMANOVSearch for more papers by this authorM. G. SAFAROV, M. G. SAFAROVSearch for more papers by this author First published: April 22, 1986 https://doi.org/10.1002/chin.198616225Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume17, Issue16April 22, 1986 RelatedInformation

ChemInform Abstract: Intramolecular Olefinic Aldehyde Prins Reactions for the Construction of Five‐ Membered Rings.

AbstractDie olefinischen Aldehyde (I) und (VI) cyclisieren in Gegenwart von Lewis‐Säuren in einer intramolekularen Prins‐Reaktion zu den Cycloalkanolen (II)‐(IV) bzw. (VII) und (VIII).

Chemistry of di- and tetrahydropyrans. Communication 6. Conjugate Prins reaction involving 4-methyl-5,6-dihydropyran

1. Reaction of 4-methyl-5,6-dihydropyran with formaldehyde and its aliphatic homologs under conditions suitable for the conjugate Prins reaction leads to the geometric isomers of 10-methyl-2-alkyl-1,3,7-trioxadecalins as the major products. 2. The stereochemistry of the reaction depends on the size of the alkyl substituent in the 2-position of the trioxadecalin ring. The trans isomers predominate up to C4, and, beginning with C6 and higher, the cis isomers are the major products.

The chemistry of di- and tetrahydropyrans. Communication 3. On the anomalous behavior of 4-Methyl-5,6-Dihydropyran in the prins reactions

1. In the reaction of formaldehyde with 2-methyl-5,6-dihydropyran and of acetaldehyde with 4-methyl-5,6-dihydropyran under Prins reaction conditions, compounds with 1,3-dioxane structure, the corresponding trioxadecalins, are formed as the main products. 2. 4-Methyl-5,6-dihydropyran reacts with CH2O anomalously with the preferential formation of diols, cis- and trans-3-hydroxyraethyl-4-hydroxy-4-methyltetrahydropyrans (1∶10). This is explained by a shift of the equilibrium in the trans-trioxadecalin-trans-diol system in the direction of the latter due to its higher thermodynamic stability. 3. The acetylation of cis- and trans-diols and also the hydrolysis and acetolysis of cis- and trans-trioxadecalins proceeds with a complete retention of the configuration.