Die permanganatoxydation von 1,5-dienverbindungen

Klein, E.; Rojahn, W.

doi:10.1016/s0040-4020(01)93889-x

Cited by 116 publications

(38 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, the 13 The stereochemistries of the cyclization products 2 and 6 were confirmed by comparison of their spectral data with those of authentic samples prepared from 1,5-dienes 1 and 5 by syn stereospecific reaction with KMnO 4 , as described for the reactions of geranyl and neryl acetates with this reagent. [9] The main products obtained from these reactions were indistinguishable ( 1 H NMR, 13 C NMR, MS) from compounds 2 and 6 obtained with RuO 4 . Thus, KMnO 4 oxidation of 1 afforded 2 in 30% yield, while reaction of 5 furnished a 50% yield of 6.…”

Section: Resultsmentioning

confidence: 84%

“…[8] In this work, it was reported that reactions of the 1,5-dienes geranyl acetate and neryl acetate with RuO 4 gave products containing a tetrahydrofuran moiety that were formed by cis oxygenation of both double bonds, [8] the reactions being analogous to the permanganate oxidations of these substrates reported in 1965 by Klein and Rojahn. [9] The 2,5-disubstituted tetrahydrofuran moiety is a structural motif that is commonly encountered in polyoxygenated natural products. [10Ϫ12] Permanganate oxidation of 1,5-dienes represents a simple procedure for the preparation of heterocyclic systems containing oxygen and has been employed in the synthesis of tetrahydrofuran moieties in molecules of biological interest such as the polyether antibiotics monensin [13,14] and ionomycin.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Reactions of 1,5-Dienes with Ruthenium Tetraoxide: Stereoselective Synthesis of Tetrahydrofurandiols

2001

View full text Add to dashboard Cite

An improved procedure for the ruthenium tetraoxide catalysed oxidation of 1,5-dienes, employing 0.05 equiv. of the catalyst RuO 2 ·2H 2 O, 2.5 equiv. of NaIO 4 as a stoichiometric oxidant, and a biphasic solvent system of AcOEt/(CH 3 ) 2 CO/ H 2 O (2:1:1, v/v/v), is presented. Reactions of 1,5-dienes 1, 3, and 5 furnished the new cis-tetrahydrofuran products 2, 4, 6, and 7 with total stereospecificity. The structures of the products have been established on the basis of NMR and MS data, as well as chemical evidence. Application of this procedure to geranyl acetate (8) and neryl acetate (12) afforded the cis-tetrahydrofuran derivatives 9, 10, and 13 in high yields, accompanied by small amounts of trans-tetrahydrofu-

show abstract

Section: Resultsmentioning

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Reactions of 1,5-Dienes with Ruthenium Tetraoxide: Stereoselective Synthesis of Tetrahydrofurandiols

2001

View full text Add to dashboard Cite

show abstract

“…Analogy for this type of process exists (23), and the formation of epoxides during permanganate oxidation has been reported else~vhere (24)(25)(26)(27)(28). I t will be recalled that methyl sandaracopimarate (IIb) underwent normal oxidation of the vinyl group to yield the acid V, whereas methyl pimarate (IB) gave tions (vapor-phase chromatography) where we could observe less than 0.5% of the epoxidized material.…”

mentioning

confidence: 54%

Diterpene chemistry. II. The preferential oxidation of the vinyl groups of pimaric and sandaracopimaric acids

ApSimon¹,

Chau²,

Craig³

et al. 1967

Can. J. Chem.

View full text Add to dashboard Cite

The use of the Lemieux -von Rudloff technique for the oxidation of the vinyl groups of pimaric (Ib) and sandaracopimaric (IIb) acid methyl esters has been investigated. Although the process leads to the expected C-13 acid V in the case of methyl sandaracopimarate, an unexpected epoxy acid was obtained from methyl pimarate. This product was shown to be the 8p,14p-epoxy-13-a-ketoacid V I I I a , probably arising from an intramolecular process during oxidation of the vinyl group.Canadian Journal of Chemistry. Volume 45, 1439Volume 45, (1967 Our interest in diterpene resin acids of the pimaric acid type (Ia, IIa) led us to consider these compounds as starting materials for the partial synthesis of other natural products; for instance, novel steroidal derivatives should be available by the formal insertion of one carbon atom, as illustrated in 111. The nuclear double bond between C-8 and C-14 and the vinyl group a t C-13 represent positions for elaboration of functions for carrying out such transformations (1). Accordingly, we studied the conversion of these groups into those more useful for ring closure.T o achieve a stepwise synthesis, different functionality was required a t the double bonds mentioned. The enhanced reactivity of the vinyl group to hydrogenation (2, 4), hydroboration (3), and hydroxylation (4) suggested that a preferential oxidation process should be possible a t that site, leading to acids of type IV. A sequence paralleling that of Edwards (4) or a similar method (5) would seem possible, but in our hands this route proved impractical since relatively large amounts of the C-13 acid could not be obtained in a high yield or in a sufficiently pure form for further studies. I t was thus decided to attempt a selective oxidation of the vinyl group; the method vie considered most amenable to variations in the reaction parameters was that of Lemieux and von Rudloff (6). This tech-niclue involves the use of a c a t a l~~t i c amount of potassium permanganate in a buffered solution of sodium metaperiodate. The double bond is attacked by the permanganate, which is continually being regenerated from its reduced state by the periodate. Any glycols or a-ketols (8-9) that are formed are then cleaved by the excess periodate present ; further oxidation of aldehydes by permanganate to acids ensues. This method was applied to the methyl esters of pimaric (Ib) and sandaracopimaric acids (IIb), and the results are described in this r e~o r t .T h e oxidation of methyl sandaracopimarate (IIb), using 4 M equivalents of periodate with t-butyl alcohol as solvent (lo), gave 55% of the ester acid V, whereas 6 equivalents of oxidant gave 85% of this product, whose structure was deduced as follows. T h e infrared spectrum showed absorption characteristic of an acid (3 100 and 1 695 cm-l) and an ester (1 735 cm-l), and the nuclear magnetic resonance (n.m.r.) spectrum showed a single unsplit peak in the olefinic region a t 4.43 T, indicating loss of the vinyl group. T h e methyl signal attributable to the C-13 methyl group (11...

show abstract

“…A convenient method for the formation of THF diols is through the oxidative cyclization of 1,5-dienes to form 2,5-disubstituted THF diols. Early work found that permanganate could mediate this process [178], but subsequent work discovered RuO 4 [179] and OsO 4 [180] could also perform this cyclization in the presence of an oxidant such as NaIO 4 . It is accepted that this transformation proceeds through sequential [3+2] cycloadditions followed by hydrolysis of the metallo ester to deliver the THF diol [181].…”

Section: Stereoselective Olefin Metathesis In Synthetic Applicationsmentioning

confidence: 99%

Recent Advancements in Stereoselective Olefin Metathesis Using Ruthenium Catalysts

2017

View full text Add to dashboard Cite

Olefin metathesis is a prevailing method for the construction of organic molecules. Recent advancements in olefin metathesis have focused on stereoselective transformations. Ruthenium olefin metathesis catalysts have had a particularly pronounced impact in the area of stereoselective olefin metathesis. The development of three categories of Z-selective olefin metathesis catalysts has made Z-olefins easily accessible to both laboratory and industrial chemists. Further design enhancements to asymmetric olefin metathesis catalysts have streamlined the construction of complex molecules. The understanding gained in these areas has extended to the employment of ruthenium catalysts to stereoretentive olefin metathesis, the first example of a kinetically E-selective process. These advancements, as well as synthetic applications of the newly developed catalysts, are discussed.

show abstract

Die permanganatoxydation von 1,5-dienverbindungen

Cited by 116 publications

References 14 publications

Reactions of 1,5-Dienes with Ruthenium Tetraoxide: Stereoselective Synthesis of Tetrahydrofurandiols

Reactions of 1,5-Dienes with Ruthenium Tetraoxide: Stereoselective Synthesis of Tetrahydrofurandiols

Diterpene chemistry. II. The preferential oxidation of the vinyl groups of pimaric and sandaracopimaric acids

Recent Advancements in Stereoselective Olefin Metathesis Using Ruthenium Catalysts

Contact Info

Product

Resources

About