Synthesis of 3-deoxy-2-uloses via the indium-mediated allylation reaction

Gintner, Manuel; Denner, Christian; Schmölzer, Christoph; Fischer, Michael B.; Frühauf, Peter; Kählig, Hanspeter; Schmid, Walther

doi:10.1007/s00706-019-02438-y

Cited by 5 publications

(3 citation statements)

References 34 publications

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“…The overall yield of the isolated epimers was 92%. According to Binder et al [17] and our own experience [18], we expected the syn -product ( 2- syn ) to be the main diastereomer. However, the determination of the configuration is not possible by NMR analysis.…”

Section: Resultsmentioning

confidence: 99%

Indium-mediated C-allylation of melibiose

Denner

Gintner

Kählig

et al. 2019

Beilstein J. Org. Chem.

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The indium-mediated allylation reaction has been applied to melibiose, a disaccharidic substrate. This elongation methodology allows for a short, efficient and diastereoselective approach towards complex glycosylated carbohydrate structures. The stereochemical outcome of the key intermediates, allylated disaccharides, has been determined by X-ray analysis. Ozonolysis of the introduced double bond yielded the unprotected elongated disaccharides in the equilibrium of the pyranoid as well as furanoid isomers in both anomeric forms, respectively. Per-O-acetylation has been performed to facilitate separation of the isomeric mixture for structural identification. The main product revealed to adopt a β-pyranoid form of the elongated unit at the reducing end of the disaccharide.

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Section: Resultsmentioning

confidence: 99%

Indium-mediated C-allylation of melibiose

Denner

Gintner

Kählig

et al. 2019

Beilstein J. Org. Chem.

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“…Ozonolysis of 30 gives 3-deoxy-D-erythro-2hexulose, a C-1 reduced analogue of a natural and essential ulosonic acid of biological interest. 44 Scheme 13. Synthesis of 3-deoxy-D-erythro-2-hexulose from 28 according to the method of Gintner et al 44…”

Section: Scheme 8 Rcm Reactions Of Homoallyl Ether 21 and Non-ether 23mentioning

confidence: 99%

“…44 Scheme 13. Synthesis of 3-deoxy-D-erythro-2-hexulose from 28 according to the method of Gintner et al 44…”

Section: Scheme 8 Rcm Reactions Of Homoallyl Ether 21 and Non-ether 23mentioning

confidence: 99%

Regiodivergent Medium-Ring Oxasilacycle Synthesis from Diallylsilanes

O’Neil¹,

Fomina²,

Myers³

et al. 2022

HETEROCYCLES

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Medium-ring (7-9 membered) oxasilacycles were synthesized by sequential electrophile-promoted rearrangement of diallylsilanes, etherification with an alkene-containing alcohol, and ring-closing metathesis (RCM). Depending on the choice of catalyst for the RCM, different oxasilacycle products could be obtained. The Grubbs first-generation catalyst cleanly afforded allyl ether oxasilacycles whereas the second-generation Grubbs catalyst selected for the regioisomeric cyclic enol ether, resulting from RCM followed by isomerization.Isomerization during RCM was suppressed by substitution at the allyl ether position.The use of homoallyl ether-or non-ether substrates, and/or the addition of benzoquinone also prevented isomerization during RCM, suggestive of a ruthenium hydride-based double bond migration mechanism. Both product subclasses represent useful synthetic intermediates. As an initial demonstration, this sequence was used to prepare the side-chain of the natural product psymberin, as well as a ulosonic acid analogue.

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