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Showing papers on "Ferrier rearrangement published in 1996"


Journal ArticleDOI
TL;DR: Two key synthetic transformations included the Ferrier rearrangement reaction to construct the optically-pure inositol skeleton and the sequential acylation of the primary and secondary hydroxyl groups on the glycerol derivatives.
Abstract: Photoactivatable analogues of 1-l-phosphatidyl-d-myo-inositol 4,5-bisphosphate (PtdIns(4,5)P2 or PtdInsP2) and the corresponding 3,4,5-trisphosphate (PtdIns(3,4,5)P3 or PtdInsP3) were prepared from the two chiral precursors, methyl α-d-glucopyranoside and 1,2-isopropylidene-sn-glycerol. Two key synthetic transformations included the Ferrier rearrangement reaction to construct the optically-pure inositol skeleton and the sequential acylation of the primary and secondary hydroxyl groups on the glycerol derivatives. The sn-1-O-(6-aminohexanoyl) PtdInsP2 and PtdInsP3 derivatives were further modified to contain benzophenone photophores in unlabeled and high specific activity tritium-labeled forms.

72 citations


Journal ArticleDOI
TL;DR: PdCl2 was found to mediate the Ferrier rearrangement of broad range of substrates catalytically in neutral conditions as mentioned in this paper, and the stereoselectivity of newly formed chiral center was controlled by the hydroxyl protective groups on the starting sugar moiety and was rationally explained by the consideration of chair like conformations.

40 citations


Journal ArticleDOI
TL;DR: A Ferrier rearrangement strategy starting from α-d-glucose gave a protected inositol, which after coupling to a chiral diacylglycerol phosphoramidite, provided a tritium-labeled, benzophenone-containing derivative of P-l-(O-aminopropyl) linked dipalmitoyl PtdIns(3,4)P2.

32 citations


Journal ArticleDOI
TL;DR: In this article, the Ferrier rearrangement of a methyl α-d -mannopyranoside derivative (8a), followed by a stereoselective reduction gave a l -chiro-inositol derivative (2), which was converted to l -myo- inositol 1,2,3-trisphosphate (3) and l -chirosin-inotransformer 1, 2,3,5-tetrakisphophosphate(4).

14 citations


Journal ArticleDOI
TL;DR: In this paper, a route to a structurally modified Dmyo-inositol 1,3,4,5-tetrakisphosphate analogue, D-2-deoxy-myo-, 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 34, 35, 36, 37, 38, 39
Abstract: A route to a novel, structurally modified D-myo-inositol 1,3,4,5-tetrakisphosphate analogue, D-2-deoxy-myo-inositol 1,3,4,5-tetrakisphosphate 3, is described, involving as the key steps a selective protection of methyl α-D-glucopyranoside and subsequent catalytic Ferrier rearrangement to a deoxyinosose. Thus, methyl α-D-glucopyranoside was converted by an improved procedure into methyl 4,6-O-benzylidene-α-D-glucopyranoside 4 and thence into methyl 3-O-benzoyl-2-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside 7 without recourse to column chromatography. Compound 7 was converted into methyl 3,4-di-O-benzoyl-2-O-benzyl-6-deoxy-α-D-xylo-hex-5-enopyranoside 12 via methyl 3,4-di-O-benzoyl-2-O-benzyl-6-bromo-6-deoxy-α-D-glucopyranoside 8. Rearrangement of enol ether 12 with mercury(II) trifluoroacetate provided (2S,3R,4S,5R)-2,3-dibenzoyloxy-4-benzyloxy-5-hydroxycyclohexanone 13 and (2S,3R,4S,5S)-2,3-dibenzoyloxy-4-benzyloxy-5-hydroxycyclohexanone 14. Attempts to invert the configuration at position 5 of compound 14 were unsuccessful, but provided a number of discrete products. Reduction of compound 13 and saponification furnished L-1-O-benzyl-3-deoxy-scyllo-inositol 23, which was phosphorylated and deprotected to give the target 3.

10 citations


Journal ArticleDOI
TL;DR: In this paper, the Ferrier rearrangement of a methyl α-d -mannopyranoside derivative (8a), followed by a stereoselective reduction gave a l -chiro-inositol derivative (2), which was converted to l -myo- inositol 1,2,3-trisphosphate (3) and l -chirosin-inotransformer 1, 2,3,5-tetrakisphophosphate(4).
Abstract: The Ferrier rearrangement of a methyl α- d -mannopyranoside derivative (8a), followed by a stereoselective reduction gave a l -chiro- inositol derivative (2), which was converted to l -chiro- inositol 1,2,3-trisphosphate (3) and l -chiro- inositol 1,2,3,5-tetrakisphosphate (4). Compounds 3 and 4 may be considered to be the C3-position stereoisomers of d -myo- inositol 1,2,6-trisphosphate (α-trinositol) and d -myo- inositol 1,3,4,5-tetrakisphosphate, respectively, and should be useful for the binding studies with their macromolecular counterparts.

1 citations


Journal ArticleDOI
TL;DR: PdCl2 was found to mediate the Ferrier rearrangement of broad range of substrates catalytically in neutral conditions as mentioned in this paper, and the stereoselectivity of newly formed chiral center was controlled by the hydroxyl protective groups on the starting sugar moiety and was rationally explained by the consideration of chair like conformations.
Abstract: PdCl2 was found to mediate the Ferrier rearrangement of broad range of substrates catalytically in neutral conditions. In this reaction, the stereoselectivity of newly formed chiral center was controlled by the hydroxyl protective groups on the starting sugar moiety and was rationally explained by the consideration of chair like conformations.