Unusual Rearrangement in the Photochemical Addition of Bis(alkylidene)disilacyclobutanes to C60

Kusukawa, Takahiro; Kabe, Yoshio; Erata, Tomoki; Nestler, B.; Andō, Wataru

doi:10.1021/om00023a022

Cited by 24 publications

(11 citation statements)

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“…Further evidence for the structure of 1 is obtained from the 29 Si-1 H HMBC spectrum ( Figure 1). [18] The signals of Q 4 and H a show a correlation, which indicates the Si À O À Si À H connectivity. The signals for T 1 and H b also show a correlation that arises from the Si À O À C À H connectivity.…”

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confidence: 99%

Nonhydrolytic Synthesis of Branched Alkoxysiloxane Oligomers Si[OSiH(OR)₂]₄ (R=Me, Et)

2010

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confidence: 99%

Nonhydrolytic Synthesis of Branched Alkoxysiloxane Oligomers Si[OSiH(OR)₂]₄ (R=Me, Et)

2010

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“…Although the silyl ether 13 was formed in 39% (the remainder of the material being 12), no doubly protected side product was detected and exclusive selectivity for the equatorial OH was observed. To confirm the structural assignment of 13, 29 Si-1 H HMBC experiments, 24 which allow for 29 Si-1 H shift correlations over two and/or three bonds, were performed (Fig. 3).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of asymmetrically substituted scyllo -inositol

Rodriguez

Walczak

2016

Tetrahedron Letters

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a b s t r a c t scyllo-Inositol, a rare member of the inositol family, is present in axinelloside A, a marine metabolite with interesting inhibitory activity against human telomerase. Here, we present a concise synthesis of asymmetrically substituted scyllo-inositol starting from inexpensive D-glucose. Our synthetic approach capitalizes on Ferrier rearrangement of vinyl acetate and stereoselective reduction of the resultant ketone to establish the scyllo-inositol core. The protocol provides access to large quantities of scyllo-inositol in 10 steps from commercially available materials. IntroductionInositols are a class of nine distinct isomers of 1,2,3,4,5,6-cyclohexanehexol in which the configuration of the hydroxyl group is permutated giving rise to seven meso and two chiral isomers. 1 Among the members of this family, myo-inositol (1) and its derivatives are the most studied inositols due to their role as secondary messengers (in the form of phosphates and pyrophosphates) and their presence in glycoconjugates (e.g., glycosylphosphatidylinositol (GPI) anchors). 2 However, scyllo-inositol (2), an isomer with all hydroxyl groups in equatorial configuration, is less explored. 1 The parent compound is found at high concentrations in human brain, 3 and has been implicated in certain neurological disorders. 1 There are numerous reports describing the use of scyllo-inositol as a potential drug targeting Alzheimer's 4 and Parkinson's diseases, 5 and research in this area is a topic of current interest. 6 For instance, orally administered scyllo-inositol inhibited the aggregation of amyloid-b (Ab) 7 and prevented the formation of insoluble amyloid fibers believed to cause neuronal dysfunction in Alzheimer's disease. Derivatives of scyllo-inositol (including fluorinated analogs 8 ) have been investigated, among which the hexaphosphate has been identified as a promising drug candidate.From the synthetic standpoint, the conversion of myo-inositol into scyllo-inositol by Kishi 9 is a practical route to prepare large quantities of symmetrical scyllo-inositol from an inexpensive starting material. 10 Other studies by Ikegami 11 and Altenbach 12 provided the parent hexols using glucose or p-quinone as the substrates. Similar to myo-inositol, phosphate esters of scyllo-inositols have been prepared synthetically. 13 Due to the C 3 symmetry of the orthoester derivatives, the hexol scaffold has been used in the preparation of glycodendrimers, 14 drug delivery compounds, 15 siderophore (enterobactin) analogs, 16 and hetero-bimetallic catalysts. 17 There is only a small number of examples in which scyllo-inositol is present in an asymmetric form, 1 and axinelloside A (5) stands out due to its intriguing chemical structure and biological activity. 18 This polysulfated oligosaccharide was isolated from a marine sponge Axinella infundibula, and its structure was proposed based on 1D and 2D NMR studies. The unique features of this molecule are the presence of ten 1,2-cis glycosidic bonds, four fatty acid chains, and the eastern part ter...

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“…Disilylcyclobutanes [67,68] and cyclotetrasilanes [68,69] react in a similar fashion. Disilylcyclobutanes [67,68] and cyclotetrasilanes [68,69] react in a similar fashion.…”

Section: Scheme 610mentioning

confidence: 90%

Radical Additions

2004

Fullerenes

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Unusual Rearrangement in the Photochemical Addition of Bis(alkylidene)disilacyclobutanes to C60

Cited by 24 publications

References 0 publications

Nonhydrolytic Synthesis of Branched Alkoxysiloxane Oligomers Si[OSiH(OR)₂]₄ (R=Me, Et)

Nonhydrolytic Synthesis of Branched Alkoxysiloxane Oligomers Si[OSiH(OR)₂]₄ (R=Me, Et)

Synthesis of asymmetrically substituted scyllo -inositol

Radical Additions

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Unusual Rearrangement in the Photochemical Addition of Bis(alkylidene)disilacyclobutanes to C60

Cited by 24 publications

References 0 publications

Nonhydrolytic Synthesis of Branched Alkoxysiloxane Oligomers Si[OSiH(OR)2]4 (R=Me, Et)

Nonhydrolytic Synthesis of Branched Alkoxysiloxane Oligomers Si[OSiH(OR)2]4 (R=Me, Et)

Synthesis of asymmetrically substituted scyllo -inositol

Radical Additions

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Nonhydrolytic Synthesis of Branched Alkoxysiloxane Oligomers Si[OSiH(OR)₂]₄ (R=Me, Et)

Nonhydrolytic Synthesis of Branched Alkoxysiloxane Oligomers Si[OSiH(OR)₂]₄ (R=Me, Et)