Beiträge zur Konstellationsanalyse, III Alkoholyse von Toluolsulfonsäureestern, V

Hückel, Walter; Bross, Richard; Fechtig, Ottraud; Feltkamp, Herbert; Geiger, Susanne; Hanack, Michael; Heinzel, Martin; Hubele, Adolf; Kurz, Jürgen; Maier, Martin E.; Maucher, Dieter; Näher, Gotthilf; Neidlein, R.; Rashingkar, Ramchandra B.

doi:10.1002/jlac.19596240113

Cited by 48 publications

(6 citation statements)

References 71 publications

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“…group in the pseudo-axial position for 3b and pseudo-equa-Dimethyldioxirane (DMD) [18] and methyltrioxorhenium (MTO) [19] were prepared according to literature procedures, as were also the torial for 3c. As for the flexible 2-cycloalkenols 2, 3a, 4, 3-alkyl-substituted cyclohexenes 1b, [20] 1c, [21] and 1d [22] and the and 5, the oxidation of the rigid 3b, c by MTO/UHP also conformationally fixed cis-and trans-5-tert-butyl-2-cyclohexenols proceeded cleanly in good yields to the syn-and anti-epox-(3b, c). [23] The cyclic alcohols 2-cyclopentenol (2), [24] 2-cyclohexides 8b, c without any enone formation (Table 3, Entries 1, enol (3a), [25] and 2-cyclooctenol (5) [26] were synthesized by pho-3, 7, 9).…”

Section: Methodsmentioning

confidence: 94%

Steric and Electronic Effects in the Diastereoselective Catalytic Epoxidation of Cyclic Allylic Alcohols with Methyltrioxorhenium (MTO)

Adam

Mitchell²,

Saha‐Möller

1999

European J Organic Chem

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The steric effects of allylic substituents in the epoxidations with methyltrioxorhenium/urea/hydrogen peroxide adduct (MTO/UHP) have been assessed for a series of 3‐alkyl‐substituted cyclohexenes. The trans selectivity increases with the size of the substituent and the diastereoselectivities follow an excellent linear correlation with the steric substituent constants of Taft (Es) or Charton (ν). Good cis selectivity is observed in the epoxidation of the cyclic allylic alcohols 2‐cyclopentenol and 2‐cyclohexenol due to a hydroxy‐directing effect through hydrogen bonding; however, for 2‐cycloheptenol and 2‐cyclooctenol hydrogen bonding is ineffective and steric interactions cause a higher trans selectivity. The conformationally fixed cis‐ and trans‐5‐tert‐butyl‐2‐cyclohexenols serve as suitable substrates for gauging the dihedral angle of the transition states for the oxygen transfer in these epoxidations. Thus, the MTO/UHP oxidant favours a quasi‐equatorial arrangement of the hydroxy group for effective hydrogen bonding (hydroxy‐group directivity), in analogy to m‐chloroperbenzoic acid (m‐CPBA) and dimethyldioxirane (DMD), and a dihedral angle of ca. 130° is suggested.

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Section: Methodsmentioning

confidence: 94%

Steric and Electronic Effects in the Diastereoselective Catalytic Epoxidation of Cyclic Allylic Alcohols with Methyltrioxorhenium (MTO)

Adam

Mitchell²,

Saha‐Möller

1999

European J Organic Chem

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“…Alkaline methanolysis of trans-2-methylcyclohexyl tosylate ( Fig. 13) yields an elimination to substitution product ratio of 75.%:25% (21).…”

Section: Solvolysis Of Bicyclic and Monocyclic Saturated Compounds: Lmentioning

confidence: 99%

“…. Hlckel, et al(21) found a ratio of elimination to substitution product of 75%:25% for solvolysis of trans-2-methylcyclohexyl tosylate in methanolic sodium methoxide. The latter reaction was run at 60°for18 days.It is apparent that the cis-pinocarvyl exocyclic double bond is the main controlling factor in the competition between elimination and substitution during solvolysis.…”

mentioning

confidence: 99%

Solvolysis of cis-pinocarvyl p-bromobenzenesulfonate and related esters

Gruenewald¹,

Johnson²

1967

J. Org. Chem.

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Brosylate 45 2-Methylenecyclohexyl Brosylate 47 Stability of Solvolysis Products 47 Acetolysis of cis-Pinocarvyl Brosylate 48 Solvolysis of Saturated Brosylates 48 Alkaline Methanolysis 48 Isopinocamphyl Brosylate 48 trans-2-Methylcyclohexyl Brosylate 50 Solvolysis of Unsaturated p-Nitrobenzoates Alkaline Methanolysis of cis-Pinocarvyl, trans-Pinocarvyl, and 2-Methylenecyclohexyl p-Nitrobenzoate Attempted Hydrolysis of cis-Pinocarvyl, trans-Pinocarvyl, and 2-Methylenecyclohexyl p-Nitrobenzoate DISCUSSION cis-Pinocarvyl Brosylate Solvolysis Mechanisms Carbon-Oxygen Cleavage and Allylic Rearrangement Lyate Ion Effect Salt Effect Solvent Effect Proposed Solvolysis Mechanisms Effect of cis-Pinocarvyl Structure on-Mechanism and Rate of Brosylate Solvolysis Effect of the Isopropylidene Bridge 62 Effect of Unsaturation 65 Effect of Leaving Group on Mechanism of Solvolysis of cis-Pinocarvyl and Related Esters Alkaline Methanolysis of Unsaturated p-Nitrobenzoates Hydrolysis of Unsaturated p-Nitrobenzoates

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“…Letzteres war mit einer durch WOLFF-KISH-NER-Reduktion von N-Methyl-6-oxo-d5~10-octahydroisochinolin (10) erhaltenen authentischen Probe identisch [3]. Die Richtung der Elimination entspricht der in der Decalin-Reihe beobachteten, indem la-Tosyloxy-trans-decalin (1 1) ebenfalls vorwiegend das trisubstituierte Olefin, namlich d1, [8] . Die Hydrierung I%ELVBTICA C H I M I C A ACTA des 5B-Bromids 8a lieferte reines N-Methyl-trans-decahydroisochinolin (6a), was die trans-Ringverkniipfung beweist.…”

unclassified

Die multiple Isomerisierung von Brom‐decahydroisochinolinen. Decahydroisochinoline. I. Teil

Grob¹,

Wohl²

1965

Helvetica Chimica Acta

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2 3 l) Vgl. die Thssertation R . A. WOHL, Base1 106.5, soxvie die Keihe Fragmenticrungs-Reaktionen. z, Substitucnten, welche auf tlcr gleichen Seite dcr Molekclcbenc stchen wie dcr Substituent an C-9 (im vorlicgenden Fall cin Wasserstoffatom) wcrdcn mit dcm Prafix B bczeichnct, die auf tler Gegcnseite mit 01. Die Ringvcrliniipfung wird \vie ublich mit trans bzw. cis gekennzeichnct. 3, I n cliescr Xrbeit [l] uurde die Konfiguration offengelassen. Uber dic Zuordnung als lop-Hvdroxy-lkrivdt wird spatcr bcrichtct ; vg!. Fussnotc I ) .

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Beiträge zur Konstellationsanalyse, III Alkoholyse von Toluolsulfonsäureestern, V

Cited by 48 publications

References 71 publications

Steric and Electronic Effects in the Diastereoselective Catalytic Epoxidation of Cyclic Allylic Alcohols with Methyltrioxorhenium (MTO)

Steric and Electronic Effects in the Diastereoselective Catalytic Epoxidation of Cyclic Allylic Alcohols with Methyltrioxorhenium (MTO)

Solvolysis of cis-pinocarvyl p-bromobenzenesulfonate and related esters

Die multiple Isomerisierung von Brom‐decahydroisochinolinen. Decahydroisochinoline. I. Teil

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