523-92-2Relevant academic research and scientific papers
Lipase Regioselective O-Acetylations of a myo-Inositol Derivative: Efficient Desymmetrization of 1,3-Di-O-benzyl-myo-inositol
Ribeiro, Marcela F. P.,Pais, Karla C.,de Jesus, Barbara S. M.,Fernandez-Lafuente, Roberto,Freire, Denise M. G.,Manoel, Evelin A.,Simas, Alessandro B. C.
, p. 386 - 391 (2018/01/27)
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.
Hydroxyl group deprotection reactions with Pd(OH)2/C: a convenient alternative to hydrogenolysis of benzyl ethers and acid hydrolysis of ketals
Murali, Chebrolu,Shashidhar, Mysore S.,Gopinath, Chinnakonda S.
, p. 4149 - 4155 (2007/10/03)
Benzyl ethers, ketals and orthoformates were cleaved with Pd(OH)2/C in methanol, to generate the corresponding alcohol; carboxylic acid esters were stable under these reaction conditions. Pd(OH)2/C in methanol was used for the deprotection of hydroxyl groups during the preparation of sequoyitol via myo-inositol orthobenzoate. This method of deprotection has the potential to be useful in the synthesis of different classes of organic compounds since the reaction conditions do not involve strong acids, bases or hydrogen.
Stereoselective oxidation of protected inositol derivatives catalyzed by inositol dehydrogenase from Bacillus subtilis
Daniellou, Richard,Phenix, Christopher P.,Tam, Pui Hang,Laliberte, Michael C.,Palmer, David R. J.
, p. 401 - 403 (2007/10/03)
Inositol dehydrogenase (EC 1.1.1.18) from Bacillus subtilis is shown to have a nonpolar cavity adjacent to the active site, allowing racemic protected inositol derivatives such as 4-O-benzyl-myo-inositol to be recognized with very high apparent stereoselectivity.
Stereochemical observations on the bromate induced monobromopentahydroxylation of benzene by catalytic photoinduced charge transfer osmylation. A concise synthesis of (±)-pinitol
Jung, Pierre M. J.,Motherwell, William B.,Williams, Alvin S.
, p. 1283 - 1284 (2007/10/03)
The use of lower temperatures in the title reaction favours the formation of the neo diastereoisomer of the deoxybromoinositol whose diisopropylidene derivative can be converted in three steps to (±)-pinitol.
An effective strategy for the synthesis of 6-O-(2-amino-2-deoxy-α-D-glucopyranosyl)-D-chiro- and -D-myo-inositol 1-phosphate related to putative insulin mimetics
Jaramillo,Chiara,Martin-Lomas
, p. 3135 - 3141 (2007/10/02)
Two glycosylinositol phosphates related to putative insulin mimetics, 6-O-(2-amino-2-deoxy-α-D-glucopyranosyl)-D-chiro-inositol 1-phosphate (1) and 6-O-(2-amino-2-deoxy-α-D-glucopyranosyl)-D-myo-inositol 1-phosphate (2), have been synthesized from selectively protected and enantiomerically pure D-chiro- and myo-inositol derivatives. The D-chiro-inositol unit was prepared in a multigram scale from D-glucose using the Ferrier's carbocyclization route, and it was transformed into the corresponding myo epimer by an oxidation-reduction sequence. The trichloroacetimidate method was applied efficiently for the key glycosylation of the inositol derivatives.
The preparation of phosphorylated intermediates for the synthesis of racemic and chiral myo-inositol 1,4,5-trisphosphate and its phosphorothioate analogues
Desai, Trupti,Fernandez-Mayoralas, Alfonso,Gigg, Jill,Gigg, Roy,Payne, Sheila
, p. 157 - 176 (2007/10/02)
Reaction of racemic 1,2,4-tri-O-benzyl-myo-inositol 3- with bis(2,2,2-trichloroethyl) phosphorochloridate gave a mixture of the 3,5- and 3,6-bisphosphate derivatives which were difficult to separate and could not be phosphorylated further.The bisphosphates were synthesised by the phosphorylation of the 5- and 6-O-(cis-prop-1-enyl) derivatives of racemic 1,2,4-tri-O-benzyl-myo-inositol and subsequent acidic hydrolysis. 1D-2,3,6-Tri-O-benzyl-1,4-di-O-(cis-prop-1-enyl)-myo-inositol was converted into crystalline 1D-2,3,6-tri-O-benzyl-myo-inositol 1,4-bis(dibenzyl phosphate), and thence into the crystalline 1,4,5-tris(dibenzyl phosphate) which was also obtained, using dibenzyloxy(diisopropylamino)phosphine, from 1D-2,3,6-tri-O-benzyl-myo-inositol.The latter compound was converted, using bis(2-cyanoethoxy)(diisopropylamino)phosphine, into the crystalline 1,4,5-tris which was also obtained from the 4,5-bis.Both the tris and the tris(dibenzyl phosphate) are intermediates suitable for the synthesis of 1,4,5-IP3.
Approaches to the synthesis of glycosyl phosphatidyl inositols. Enantioselective synthesis of optically active chiro- and myo-inositols
Jaramillo,Martin-Lomas
, p. 2501 - 2504 (2007/10/02)
An efficient synthetic strategy to optically active conveniently substituted D-chiro (5) and D-myo-inositol (10) derivatives has been developed starting from methyl α-D-glucopyranoside. Compounds 5 and 10 constitute valuable intermediates for the preparation of glycosyl phosphatidyl inositols.
Mikrobial Oxidation in Synthesis: Preparation of (+)- and (-)-Pinitol from Benzene
Ley, Steven V.,Sternfeld, Francine
, p. 3463 - 3476 (2007/10/02)
Microbial oxidation with Pseudomonas putida of benzene affords cis-1,2-dihydroxycyclohexa-3,5-diene (2) which may be converted in five steps and 49percent overall yield to (+/-)-pinitol.Resolution of an intermediate alcohol (6) with menthoxyacetyl chloride provides optically pure materials which may be independently transformed to (+)- or (-)-pinitol.Demethylation conditions for pinitol together with further reactions of (2) and related compounds were investigated.
STEREOCONFIGURATION OF SEQUOYITOL BY HIGH RESOLUTION 1H NMR
Mukherjee, R.,Medeiros, Cleane L. C. de
, p. 279 - 281 (2007/10/02)
The stereoconfiguration of sequoyitol, isolated as the pentaacetate from the leaves of Podocarpus sellowii, has been established by comparing its 1H NMR spectrum with that of myo-inositol hexaacetate.Key Word Index - Podocarpus sellowii; Podocarpaceae; sequoyitol; 5-methoxy-myo-inositol; myo-inositol.
The Allyl Group for Protection in Carbohydrate Chemistry. Part 18. Allyl and Benzyl Ethers of myo-Inositol. Intermediates for the Synthesis of myo-Inositol Triphosphates
Gigg, Jill,Gigg, Roy,Payne, Sheila,Conant, Robert
, p. 423 - 430 (2007/10/02)
Racemic 1,2:4,5-di-O-isopropylidene-myo-inositol was converted into racemic 1,2,4-tri-O-benzyl-myo-inositol, 1,2,4-tri-O-p-methoxybenzyl-myo-inositol and 2,4,5-tri-O-benzyl-myo-inositol using allyl groups for 'temporary' protection.The benzyl ethers are required as intermediates for the synthesis of the 'second messenger', inositol 1,4,5-triphosphate and its metabolite, inositol 1,3,4-triphosphate. 1,2,3,4-Tetra-O-benzyl-myo-inositol, and its two monoallyl and monoprop-1-enyl ethers, were also prepared as model compounds for phosphorylation studies of the vicinal 5,6-diol system which occurs in 1,2,4-tri-O-benzyl-myo-inositol.
