- An efficient route to optically active inositol derivatives via the resolution of myo-inositol 1,3,5-orthoformate: A short synthesis of D-myo-inositol-4-phosphate
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An efficient method for the resolution of myo-inositol 1,3,5-orthoformate has been developed. The triol, 1 was converted to diastereomers via reaction with (S)-O-acetylmandeloyl chloride. Conditions were optimized for a diastereomeric ratio of 7:3. Both t
- Sureshan, Kana M.,Watanabe, Yutaka
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- Clues from crystal structures pave the way to access chiral myo-inositol derived versatile synthons: Resolution of racemic 4?O?Allyl-myo-Inositol-1,3,5-orthoesters via corresponding dicamphanates by crystallization
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Racemic 4-O-allyl-myo-inositol-1,3,5-orthoest-ers were resolved as the corresponding diastereomeric dicamphanates by crystallization from alcoholic solvents. Crystals of the two diastereomers of myo-inositol orthoacetate and one diastereomer each of myo-inositol orthoformate and myo-inositol orthobenzoate were obtained in >99% purity, on gram scale. The configuration of all these diastereomers was established by conversion to known chiral myo-inositol derivatives as well as by single crystal structure analysis. It is interesting to note that the procedures for the separation of diastereomeric myo-inositol orthoesters could be evolved due to the knowledge of crystal growth and crystal structures of inositol derivatives of comparable molecular structures. Due to the synthetic versatility of myo-inositol orthoesters, the methods described provide rapid and convenient access to a variety of chiral inositol derivatives with high synthetic potential.
- Patil, Nivedita T.,Shashidhar, Mysore S.,Tamboli, Majid I.,Gonnade, Rajesh G.
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p. 5432 - 5440
(2018/03/02)
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- Chiral desymmetrisation of myo-inositol 1,3,5-orthobenzoate gives rapid access to precursors for second messenger analogues
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Chiral desymmetrisation of myo-inositol 1,3,5-orthobenzoate via the formation of diastereoisomeric bis[(1S)-(-)-camphanate] esters provides a convenient and fast route to precursors for biologically important inositol phosphates and lipids, and to synthet
- Riley, Andrew M.,Godage, H. Yasmin,Mahon, Mary F.,Potter, Barry V. L.
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p. 171 - 174
(2007/10/03)
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- Sulfonate protecting groups: Synthesis of D- and L-myo-inositol-1,3,4,5-tetrakisphosphate precursors by a novel silver(I) oxide-mediated O-alkylation of 2,4(6)-di-O-acyl-6(4)-O-sulfonyl-myo-inositol 1,3,5-orthoformate derivatives through intramolecular assistance of the sulfonyl group
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Alkylation of racemic 2,4-di-O-acyl-6-O-sulfonyl-myo-inositol 1,3,5-orthoformates mediated by silver(I) oxide affords the corresponding racemic 2,4-di-O-alkyl-6-O-sulfonyl-myo-inositol 1,3,5-orthoformates in good yields. Control experiments suggest that these unusual reactions are due to intramolecular assistance by the sulfonyl group. O-Alkylation reactions of myo-inositol 1,3,5-orthoformate derivatives provide a new route for the synthesis of important ether derivatives of myo-inositol, which are intermediates for the preparation of phosphoinositols. The utility of this method is demonstrated by the preparation of D- and L-2,4-di-O-benzyl-myo-inositols, which were obtained by benzylation of 2,4-di-O-benzoyl-6-O-camphorsulfonyl-myo-inositol 1,3,5-orthoformate and 2,6-di-O-benzoyl-4-O-camphorsulfonyl-myo-inositol 1,3,5-orthoformate. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Sureshan, Kana M.,Das, Tanya,Shashidhar, Mysore S.,Gonnade, Rajesh G.,Bhadbhade, Mohan M.
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p. 1035 - 1041
(2007/10/03)
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- Sulfonate protecting groups. Regioselective sulfonylation of myo-inositol orthoesters-improved synthesis of precursors of D- and L-myo-inositol 1,3,4,5-tetrakisphosphate, myo-inositol 1,3,4,5,6-pentakisphosphate and related derivatives.
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The regioselectivity of sulfonylation of myo-inositol orthoesters was controlled by the use of different bases to obtain the desired sulfonate. Monosulfonylation of myo-inositol orthoesters in the presence of one equivalent of sodium hydride or triethylamine resulted in the sulfonylation of the 4-hydroxyl group. The use of pyridine as a base for the same reaction resulted in sulfonylation of the 2-hydroxyl group. Disulfonylation of these orthoesters in the presence of excess sodium hydride yielded the 4,6-di-O-sulfonylated orthoesters. However, the use of triethylamine or pyridine instead of sodium hydride yielded the 2,4-di-O-sulfonylated orthoester. Sulfonylated derivatives of myo-inositol orthoesters were stable to conditions of O-alkylation but were cleaved using magnesium/methanol or sodium methoxide in methanol to regenerate the corresponding myo-inositol orthoester derivative. These new methods of protection-deprotection have been used: (i) for the efficient synthesis of enantiomers of 2,4-di-O-benzyl-myo-inositol, which are precursors for the synthesis of D- and L-myo-inositol 1,3,4,5-tetrakisphosphate; (ii) for the preparation of 2-O-benzyl-myo-inositol which is a precursor for the preparation of myo-inositol 1,3,4,5,6-pentakisphosphate.
- Sureshan, Kana M,Shashidhar, Mysore S,Praveen, Thoniyot,Gonnade, Rajesh G,Bhadbhade, Mohan M
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p. 2399 - 2410
(2007/10/03)
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- Sulfonate protecting groups. Regioselective O-sulfonylation of myo-inositol orthoesters
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Sulfonylation of myo-inositol 1,3,5-orthoesters with alkyl or aryl sulfonyl chlorides in the presence of sodium hydride gives the corresponding 4,6-di-O-sulfonates in good yields. These sulfonates can be cleaved with magnesium in methanol to generate the free myo-inositol derivative. This methodology was used for the preparation of racemic 2,4-di-O-benzyl-myo-inositol and 2-O-benzyl-myo-inositol, which are precursors for some phosphoinositols.
- Sureshan, Kana M.,Shashidhar, Mysore S.
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p. 3037 - 3039
(2007/10/03)
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- Chemo-enzymatic synthesis of both enantiomers of myo-inositol 1,3,4,5-tetrakisphosphate
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D-Ins(1,3,4,5)P4 and unnatural L-Ins(1,3,4,5)P4 were prepared in gram-quantities from D- and L-2,6-di-O-benzyl-myo-inositol by a chemical phosphorylation and deprotection step in high yield and purity without extensive purification.
- Laumen, Kurt,Ghisalba, Oreste
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p. 1374 - 1377
(2007/10/03)
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- The preparation of racemic and enantiomerically pure myo-inositol derivatives as intermediates for the synthesis of phosphatidylinositol 3-, 3,4-bis-, and 3,4,5-tris-phosphates and for the synthesis of analogues of 1D-myo-inositol 1,3,4,5-tetrakisphosphat
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Details of the products obtained by the tin-mediated allylation and benzylation of 1,2-O-isopropylidene-myo-inositol, which were previously described in a preliminary communication, are provided here. Some of the products from these reactions, particularl
- Desai, Trupti,Gigg, Jill,Gigg, Roy,Martin-Zamora, Eloisa
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- The preparation and phosphorylation of 2,5- and 1D-2,6-di-O-benzyl-myo-inositol
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1,3,4,6-Tetra-O-allyl-myo-inositol was converted into the 2,5-di-O-benzyl- and 2,5-di-O-p-methoxybenzyl ethers, and the products were deallylated to give the 2,5-di-O-benzyl (and p-methoxybenzyl) ethers of myo-inositol, which were converted into the mono-
- Desai,Gigg,Gigg,Payne
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- An efficient chemoenzymic access to optically active myo-inositol polyphosphates
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The 1,4,5-tris-, 1,3,4-tris-, and 1,3,4,5-tetrakis-phosphates of 1D-myo-inositol have been prepared in their enantiomerically pure forms from the two enantiomers of 1,2:5,6-di-O-cyclohexylidene-myo-inositol. A facile enzymic preparation is also described
- Gou,Liu,Chen
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- AN EFFICIENT ROUTE TO D-MYO-INOSITOL 1,3,4-TRIPHOSPHATE AND D-MYO-INOSITOL 1,3,4,5-TETRAKISPHOSPHATE
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Multigram quantities of the title compounds in their enantiomerically-pure forms have been prepared by employing a chiral precursor which can be obtained via a facile enzymatic process.
- Gou, Da-Ming,Chen, Ching-Shih
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p. 721 - 724
(2007/10/02)
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- Easy access of optically active myo-inositol derivatives by enantioselective acylation using a tartatic acid monoester
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An L- or D-tartaric acid monoester is shown to be an excellent chiral auxiliary for asymmetric esterification of myo-inositol derivatives and one of the resultant esters with high optical purity is utilized for a short-step and practival synthesis of D-my
- Watanabe,Oka,Shimizu,Ozaki
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p. 2613 - 2616
(2007/10/02)
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- The Total Synthesis of myo-Inositol Phosphates via myo-Inositol Orthoformate
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Novel selective alkylations of myo-inositol orthoformate (4) have been used to prepare a series of protected myo-inositol derivatives, (5a-e), (7), (10), (12), and (16).These intermediates have been used in efficient total syntheses of myo-inositol 2-phosphate, (9); myo-inositol 4-phosphate, (6); myo-inositol 1,3-bisphosphate, (18); and myo-inositol 1,3,4,5-tetrakisphosphate (14).This report represents the first total synthesis of the important natural metabolites (14) and (18) and significantly improved methods of preparation of (6) and (9).
- Billington, David C.,Baker, Raymond,Kulagowski, Janusz J.,Mawer, Ian M.,Vacca, Joseph P.,et al.
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p. 1423 - 1429
(2007/10/02)
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- TOTAL SYNTHESIS OF OPTICALLY ACTIVE MYO-INOSITOL 1,4,5-TRISPHOSPHATE AND MYO-INOSITOL 1,3,4,5-TETRAKISPHOSPHATE
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A convenient approach to the preparation of the title compounds illustrating selective protection, optical resolution and phosphorylation is presented.
- Dreef, C. E.,Tuinman, R. J.,Elie, C. J. J.,Marel, G. A. van der,Boom, J. H. van
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p. 395 - 397
(2007/10/02)
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