The preparation, resolution, and phosphorylation of some benzyl ethers of myo-inositol: Intermediates for the synthesis of myo-inositol phosphates of the phosphatidylinositol cycle

Desai, Trupti; Gigg, Jill; Gigg, Roy; Payne, Sheila

doi:10.1016/s0008-6215(00)90497-x

Cited by 21 publications

(22 citation statements)

References 23 publications

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“…The exposed 6-hydroxyl group was then benzylated to give d -1,4-di- O -allyl-2,3,5,6-tetra- O -benzyl- myo -inositol ( 21 ). Gigg et al . prepared racemic 21 as a syrup; however, in our hands, chiral 21 was a low melting point solid.…”

Section: Resultsmentioning

confidence: 58%

“…To establish the absolute configuration for d -2,3,5-tri- O -benzyl- myo -inositol ( 13a ) a search was carried out to find a related target compound that could be synthesized in a small number of steps. Since the enantiomers of d - and l -1,2,4,5-tetra- O -benzyl- myo -inositol have been well characterized by Gigg and co-workers by selective benzylation of the known derivatives d - and l -2,4,5-tri- O -benzyl- myo -inositol, respectively, we chose one of the former pair as a reference.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis of d- and l-myo-Inositol 1,4,6-Trisphosphate, Regioisomers of a Ubiquitous Second Messenger

Mills

Potter

1996

J. Org. Chem.

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A regioisomer of the second messenger D-myo-inositol 1,4,5-trisphosphate [D-Ins(1,4,5)P(3), 1], DL-myo-inositol 1,4,6-trisphosphate [DL-Ins(1,4,6)P(3), 4ab], together with the chiral antipodes D-Ins(1,4,6)P(3)(4a) and L-Ins(1,4,6)P(3)(4b), was synthesized from myo-inositol. The racemic diol 6, after removal of the trans-ketal of fully protected 5 was p-methoxybenzylated to give the 6-O-alkylated derivative 9, as the major product in 52% yield. Gentle acidic hydrolysis of 9, followed by benzylation of the resulting triol, gave the fully protected compound 11ab. Isomerization of the two allyl groups followed by acidic hydrolysis of the resulting cis-prop-1-enyl moieties and the p-methoxybenzyl group gave the triol 13ab. Phosphorylation of 13ab followed by deprotection of the resulting compound, 14ab, with sodium in liquid ammonia and purification by ion exchange chromatography provided 4ab in 60% yield. The intermediate 9 was converted into the cis-diol 16ab in two steps. Selective acylation at the equatorial hydroxyl group using (S)-(+)-O-acetylmandelic acid in the presence of DCC and DMAP provided two diastereoisomers, 18 and 19, which were separated by flash chromatography. Further transformations provided the corresponding D- and L-1,4,6 triols, 13a and 13b, respectively, and phosphorylation, followed by deprotection of the fully blocked products as for the racemic 4ab, gave 4a and 4b, respectively. The absolute configuration of fully protected 11a was determined by transformation to the known compound L-1,2,4,5-tetra-O-benzyl-myo-inositol (22). Compound 4a was a full agonist at the platelet Ins(1,4,5)P(3) receptor for Ca(2+) release, but 4b was devoid of activity.

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Section: Resultsmentioning

confidence: 58%

Section: Resultsmentioning

confidence: 99%

Synthesis of d- and l-myo-Inositol 1,4,6-Trisphosphate, Regioisomers of a Ubiquitous Second Messenger

Mills

Potter

1996

J. Org. Chem.

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“…The establishment of the configuration of product 2 as l was carried out through its conversion into a known derivative. We initially chose to convert acetate 2 into the known derivative 5,6‐di‐ O ‐methyl‐ myo ‐inositol . However, the Ag 2 O‐mediated O ‐methylation of l ‐(+)‐ 2 did not lead to the desired diether 4 , but to a mixture of monoethers 5a and 5b .…”

Section: Resultsmentioning

confidence: 99%

Lipase RegioselectiveO‐Acetylations of amyo‐Inositol Derivative: Efficient Desymmetrization of 1,3‐Di‐O‐benzyl‐myo‐inositol

et al. 2018

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Chiral myo‐inositol derivatives play key roles in cell‐signaling processes. Despite the relevance of these compounds, few syntheses of them rely on enantioselective catalytic reactions. Even fewer reports describe the use of desymmetrization of myo‐inositol derivatives. In fact, most routes involve resolution by derivatization. Thus, a symmetrical partially protected myo‐inositol derivative, 1,3‐di‐O‐benzyl‐myo‐inositol (1), was used as a substrate in fast lipase‐catalyzed desymmetrization reactions. Among the lipases tested, both Lipozyme RM‐IM and Lipozyme TL‐IM were effective in catalyzing the formation of the chiral acetate l‐(+)‐6‐O‐acetyl‐1,3‐di‐O‐benzyl‐myo‐inositol [l‐(+)‐2] with high conversion (98–99 %) and ee (>99 %). Conversely, Novozyme 435 and Lipomod 34P as biocatalysts showed different regioselectivity, leading to the formation of the symmetrical 5‐O‐acetylated product. We were able to reuse TL‐IM lipase seven times without any noticeable decrease in the conversion. Acetate l‐(+)‐2 is a potential precursor of biologically active myo‐inositol derivatives and other relevant materials for cell biology studies.

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“…Chemoselective benzylation of the 3-position was readily effected via the in situ generated stannane acetal in the presence of tetrabutylammonium bromide and benzyl bromide in refluxing acetonitrile. Using these conditions developed by Gigg et al, 17 the ratio of 3benzyl : 4-benzyl was approximately 4 : 1 as judged from 1 H NMR analysis. It should be noted that preformation of the cyclic stannane acetal, followed by benzylation in the presence of CsF in DMF, 18 resulted in a lower yield and selectivity.…”

Section: Synthesis Of Ptdins(45)pmentioning

confidence: 99%

Synthesis and biological evaluation of a PtdIns(4,5)P2 and a phosphatidic acid affinity matrixDedicated to the memory of the late Professor Roy Gigg.

Lim

Thuring

Holmes

et al. 2002

J. Chem. Soc., Perkin Trans. 1

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The preparation, resolution, and phosphorylation of some benzyl ethers of myo-inositol: Intermediates for the synthesis of myo-inositol phosphates of the phosphatidylinositol cycle

Cited by 21 publications

References 23 publications

Synthesis of d- and l-myo-Inositol 1,4,6-Trisphosphate, Regioisomers of a Ubiquitous Second Messenger

Synthesis of d- and l-myo-Inositol 1,4,6-Trisphosphate, Regioisomers of a Ubiquitous Second Messenger

Lipase RegioselectiveO‐Acetylations of amyo‐Inositol Derivative: Efficient Desymmetrization of 1,3‐Di‐O‐benzyl‐myo‐inositol

Synthesis and biological evaluation of a PtdIns(4,5)P2 and a phosphatidic acid affinity matrixDedicated to the memory of the late Professor Roy Gigg.

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