114419-12-4Relevant articles and documents
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
Sureshan, Kana M.,Das, Tanya,Shashidhar, Mysore S.,Gonnade, Rajesh G.,Bhadbhade, Mohan M.
, p. 1035 - 1041 (2003)
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.
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.
Sureshan, Kana M,Shashidhar, Mysore S,Praveen, Thoniyot,Gonnade, Rajesh G,Bhadbhade, Mohan M
, p. 2399 - 2410 (2002)
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.
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
Patil, Nivedita T.,Shashidhar, Mysore S.,Tamboli, Majid I.,Gonnade, Rajesh G.
, p. 5432 - 5440 (2017)
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.
Access to enantiomeric organic compounds with potential for synthesis via racemic conglomerates: Inositol derivatives as a case in point
Gonnade, Rajesh G.,Patil, Madhuri T.,Patil, Nivedita T.,Sarkar, Nitai,Shashidhar, Mysore S.
, p. 3786 - 3797 (2021)
The crystal structure database was used to identify inositol derivatives that could be crystallizing as racemic conglomerates. Among the six racemic inositol derivatives identified, racemic 4-O-tosyl-6-O-benzyl-myo-inositol-1,3,5-orthoformate (A) was foun
Yb(OTf)3-Catalyzed Desymmetrization of myo-Inositol 1,3,5-Orthoformate and Its Application in the Synthesis of Chiral Inositol Phosphates
Padiyar, Laxmansingh T.,Zulueta, Medel Manuel L.,Sabbavarapu, Narayana Murthy,Hung, Shang-Cheng
, p. 11418 - 11430 (2017/11/10)
A variety of inositol phosphates including myo-inositol 1,4,5-trisphosphate, which is a secondary messenger in transmembrane signaling, were selectively synthesized via Yb(OTf)3-catalyzed desymmetrization of myo-inositol 1,3,5-orthoformate using a proline-based chiral anhydride as an acylation precursor. The investigated catalytic system could regioselectively differentiate the enantiotopic hydroxy groups of myo-inositol 1,3,5-orthoformate in the presence of a chiral auxiliary. This key step to generate a suitably protected chiral myo-inositol derivatives is described here as a unified approach to access inositol phosphates.
Sulfonate protecting groups. Regioselective O-sulfonylation of myo-inositol orthoesters
Sureshan, Kana M.,Shashidhar, Mysore S.
, p. 3037 - 3039 (2007/10/03)
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.
Chemo-enzymatic synthesis of both enantiomers of myo-inositol 1,3,4,5-tetrakisphosphate
Laumen, Kurt,Ghisalba, Oreste
, p. 1374 - 1377 (2007/10/03)
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.
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
Desai, Trupti,Gigg, Jill,Gigg, Roy,Martin-Zamora, Eloisa
, p. 97 - 133 (2007/10/03)
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
Efficient chemoenzymatic synthesis of D-myo-inositol 1,4,5-triphosphate, D-myo-inositol 1,3,4-triphosphate, and D-myo-inositol 1,3,4,5-tetraphosphate
-
, (2008/06/13)
Multigram quantities of Ins(1,4,5) P3, Ins(1,3,4) P3, and Ins(1,3,4,5)P4 are prepared in their enantiomerically pure forms from the two enantiomers of 1,2:5,6-di-O-cyclohexylidene myo-inositol. Also, a facile enzymatic preparation is also described of these chiral precursors through enantiospecific deacylation of the corresponding racemic esters is disclosed.
The preparation and phosphorylation of 2,5- and 1D-2,6-di-O-benzyl-myo-inositol
Desai,Gigg,Gigg,Payne
, p. 65 - 79 (2007/10/02)
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-
