Trimethylaluminium promoted rearrangements of unsaturated sugars into cyclohexanes

Cai, Jia; Pearce, Alan J.; Blériot, Yves; Zhang, Yongmin; Zhang, Lihe; Sollogoub, Matthieu; Sînaÿ, Pierre

doi:10.1016/j.tetasy.2003.11.029

Cited by 18 publications

(8 citation statements)

References 18 publications

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“…There are three general synthetic approaches to prepare inositols: 1) stereoselective elaborations of the inexpensive, commercially available myo -inositol [8–13]; 2) elaboration of the six carbon atom skeleton of either a) tetrahydroxycyclohexene derivatives [14–15] (synthetic or natural conduritols) through stereoselective cis-hydroxylation or epoxidation–hydrolysis of the double bond or b) benzene [16–17] or halo-benzenes [18–21], by microbial oxidation; 3) carbocyclization involving organometallic intermediates (Ferrier II reaction [22] performed on 6- O -acyl-hex-5-enopyranosides followed by reduction [23–24]; trialkylaluminium [25–26] or titanium(IV)-assisted [27] conversion of hex-5-enopyranosides and SmI 2 -promoted [28–30] pinacol coupling of dialdehyde derivatives).…”

Section: Introductionmentioning

confidence: 99%

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

D’Andrea

Catelani

Guazzelli

et al. 2016

Beilstein J. Org. Chem.

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The intramolecular aldol condensation of aldohexos-5-ulose derivatives of the D-xylo and L-ribo stereoseries has been studied. Only one of the four possible inososes was isolated from both stereoseries in reasonable yields (30–38%). The results obtained, together with the previous findings for the L-arabino and L-lyxo stereoseries, allowed for the rationalisation of a mechanism of the reaction based on open-transition-state models and electron-withdrawing inductive effects. Complementary reductions of the intermediate inososes were possible by changing the reaction conditions, and two isomeric inositol derivatives were obtained with complete stereoselection from each inosose. The presented approach permits us to control the configuration of three out of the six stereocentres of the inositol frame and gives access to seven of the nine inositols. Noteworthy, for the D-xylo derivative, the two-step sequence (condensation followed by reduction with NaBH(OAc)3) represents the biomimetic synthesis of myo-inositol. Furthermore, the sugar-based pathway leads directly to enantiomerically pure selectively protected inositols and does not require any desymmetrisation procedure which is needed when myo-inositol and other achiral precursors are employed as starting materials. As an example of application of the method, the indirect selective protection of secondary inositols’ hydroxy functions, by placing specific protecting groups on the aldohexos-5-ulose precursor has been presented.

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Section: Introductionmentioning

confidence: 99%

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

D’Andrea

Catelani

Guazzelli

et al. 2016

Beilstein J. Org. Chem.

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“…84 Treatment of the exo-glycal rearrangement precursors with trimethylaluminium instead of TIBAL gave a rearrangement to cyclohexane products with no debenzylation observed. 85 Here though, a methyl group was added from the reagent (rather than a hydride from TIBAL), giving a carbahexopyranose (287), again with stereoselectivity for the C-1-axial product (Scheme 15).…”

Section: Other Methods For Ether-linked Carbadisaccharide Synthesismentioning

confidence: 99%

Synthesis of carbasugar-containing non-glycosidically linked pseudodisaccharides and higher pseudooligosaccharides

Cumpstey

2009

Carbohydrate Research

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“…As shown in Scheme 1, two precursors 16 and 17 were easily prepared from compound 15 in a similar manner to the published procedure. 14 To carry out the rearrangement, various metal catalysts, including PdCl 2 , HgCl 2 , Hg(OAc) 2 and Hg(OCOCF 3 ) 2 , were screened. Considering the yield, stereoselectivity, and rate of reaction, we decided to use Hg(OCOCF 3 ) 2 (0.1 equivalent) as the catalyst.…”

Section: Synthesis Of 2-dos and Its Analogues As Glycosyl Acceptorsmentioning

confidence: 99%

Synthesis of neamine-derived pseudodisaccharides by stereo- and regio-selective functional group transformations

et al. 2009

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Neamine is normally found as a core structure of aminoglycoside antibiotics. In order to understand the relationship between the antibiotic activity and the configurations of the functional groups of neamine, a series of novel neamine analogues with functional group manipulations on the 2-deoxystreptamine (2-DOS) ring or the sugar ring were designed and synthesized. The synthetic approach involved the construction of 2-DOS derivatives by catalytic Ferrier II rearrangement, stereo- and regio-selective functional group transformations, glycosyl coupling reaction, and global deprotection. Of the synthetic neamine analogues, four compounds showed comparable 16S rRNA binding affinities with neamine, whereas they displayed lower binding affinities towards 18S rRNA than neamine, implying a lower toxicity to mammals. This strategy might have applications in the chemical synthesis of other neamine derivatives and new aminoglycoside antibiotics with improved biological activities.

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Trimethylaluminium promoted rearrangements of unsaturated sugars into cyclohexanes

Cited by 18 publications

References 18 publications

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

Synthesis of carbasugar-containing non-glycosidically linked pseudodisaccharides and higher pseudooligosaccharides

Synthesis of neamine-derived pseudodisaccharides by stereo- and regio-selective functional group transformations

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