Sur la configuration de l'inosite inactive

“…[20]) zur Ermittlung des Substituentenmusters heranzuziehen. Im vorliegenden Fall lassen sich die chemischen Verschiebungen der aromatischen Protonen 2-, 4-, 5-und 7-H der Komponente 10, von denen 5-und 7-H mit 7(5,7) ~ 2,5 Hz als saubere Dubletts erscheinen und 2-sowie 4-H mit 7(2,4) ~ 1,6 Hz wegen der Fernkopplungen zu den Protonen im Substituenten an C-3 breitere Signale aufweisen, mit denen ihrer unblockierten Stammverbindungen, dem Citreorosein 11 [21,22] …”

unclassified

Synthesen von Emodinaldehyd [1] / Synthesis of Emodine Aldehyde [1]

Thiem

Wessel

1985

Zeitschrift Für Naturforschung B

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9By chromium trioxide oxidation and subsequent acid hydrolysis triacetyl emodine (3) was transferred to the aldehyde in a two-step synthesis. In a more favourable sequence 3 was reacted to the bromomethyl derivative 4 and this solvolyzed to the citreoroseine derivative 5. A second NBS reaction gave 8 which after acid hydrolysis led to emodine aldehyde (9). This five-step process proceeded without chromatographic separation in 27% overall yield.

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“…: 2 (0:: (3) 5Hx3,Phx3),2Hx3,IH,J5,s=4.2 Hz,3.86 (d,lH,h.4=7.6 .Hz,3.70 (dd,lH,h5=7.8 Hz,2.75 (dd,lH,1H,J S ,s,=15.4 Hz,, 2.55 (bs, 1H, OH), 1.57 (s, 3H, C-Me). 19, and 1730 cm-1 (C=O); IHNMR (FX-200) 8=7. 5Hx3,Phx3),4.80 (s,2H,2Hx2,4.26 (d,1H,h,4=8.5 Hz,lH,3.79 (dd,lH,J4,5=2.9 Hz,2.81 (dd,lH,J5,s=5.4 Hz,2.59 (dd,1H,J e ,s,=14.4 Hz, H-6'), 1.50 (s,3H,CMe).…”

Section: Methodsmentioning

confidence: 99%

“…The physical data concerning the hexaacetate of 4 was identical with that reported for the hexaacetate of mytilitol. 19 ) In a similar manner as mentioned above, 25 may also be useful for the synthesis of 4.…”

Section: --C-)----;··mo·~~hmentioning

confidence: 94%

Syntheses of Optically Active 2,3,6-Tri-O-benzyl-d-myo-inositol, Laminitol, and Mytilitol from d-Glucose

Sato¹,

Bokura²,

Taniguchi³

1994

Bulletin of the Chemical Society of Japan

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2,3,6-Tri-O-benzyl-D-myo-inositol, which is a key intermediate of D-inositol 1,4,5-triphosphate, was synthesized from D-glucose without performing any optical resolution by utilizing C2 symmetry. Laminitol and mytilitol were also synthesized from D-glucose via the same key intermediate, 1D-{1,3/2,4)-tetra-O-benzyl-2-Cmethyl-5-cyclohexene-1,2,3,4-tetrol.Since the discovery of the role of o-myo-inositol 1,4, 5-triphosphate (IP3, 1) as an intracellular second messenger for calcium mobilization,l) the biological interest in IP 3 has greatly increased. In order to explore the biochemical process, a simple, general, and efficient methodology for the chemical syntheses of 1 and its derivatives is required that will act as agonists in the phosphoinositide system. 2) The biological importance of other stereoisomers of inositol is less well established. 3 ) However, there are two known naturally-occurring Cmethyl inositols, both isolated from algae: (-)-laminitol (3) and mytilitol (4) (Chart 1). Compound 3 is especially interesting in that it has the myo-inositoltype configuration with a methyl group at C-4, and that it inhibits the growth of Neurospora crassa. 4 ) Syntheses of racemic laminitol from myo-inositol 5 ) and (-)-laminitol from toluene 6l have been reported. To date, however, for the syntheses of 1 and its derivatives, naturally occurring cyclitol derivatives, myo-inositol,7) quebrachitol,8) and quinic acid 9 ) have been mainly used as the starting materials. In general, optical resolution has been required in the case of using myo-inositol, which has a plane of symmetry. We now report on novel synthetic methods of optically active laminitol and mytilitol, as well as details concerning a communication10) about 2,3,6-tri-0-benzyl-o-myo-inositol (2) from o-glucose, respectively. (5) was prepared from o-glucose in 56% yield (3 steps) (Scheme 1). 6-Deoxyhex-5-enopyranoside derivative (6) was synthesized by the treatment of 5 with sodium iodide, tetrabutylammonium iodide, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and molecular sieves 4A in dimethyl sulfoxide (DMSO) at 90 DC (one-pot reaction, 63% yield). Detosylation of 6, followed by protection with a benzyl group, gave methyl 2-0-benzyl-6-deoxy-3,4-bis( 0-methoxymethyl)-Q-0-xylo-hex-5-enopyranoside (8) in 87% yield (2 steps). A Ferrier reaction of 8 gave a partially protected 2,3,4,5-tetrahydroxycyclohexanone derivative, which was treated with acetic anhydride in pyridine to give the corresponding enone derivative (9) in 77% yield (2 steps). The reduction of 9 with sodium tetrahydroborate--cerium (III) chloride in dichloromethane-ethanol (1: 2), followed by benzylation of the hydroxyl group gave the protected cyclohexenol derivative (10) in 89% yield (2 steps). Oxidation of 10, which has a C 2 symmetry axis, 11) with osmium tetraoxide gave a partially protected myo-inositol derivative (11) in 83% yield. The regioselective protection of the vicinal hydroxyl groups of 11 by using dibutyltin oxide and chloromethyl methyl ether, followed by benzylation of the remain...

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Sur la configuration de l'inosite inactive

Cited by 65 publications

References 12 publications

Flexible Stereo‐ and Regioselective Synthesis of myo‐Inositol Phosphates(Part 1): Via Symmetrical Conduritol B Derivatives

Flexible Stereo‐ and Regioselective Synthesis of myo‐Inositol Phosphates(Part 1): Via Symmetrical Conduritol B Derivatives

Synthesen von Emodinaldehyd [1] / Synthesis of Emodine Aldehyde [1]

Syntheses of Optically Active 2,3,6-Tri-O-benzyl-d-myo-inositol, Laminitol, and Mytilitol from d-Glucose

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