Document Detail


Unambiguous total synthesis of the enantiomers of myo-inositol 1,3,4-trisphosphate: 1L-myo-inositol 1,3,4-trisphosphate mobilizes intracellular Ca2+ in Limulus photoreceptors.
MedLine Citation:
PMID:  7966153     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
Syntheses of the enantiomers of myo-inositol 1,3,4-trisphosphate are described. 1,4-Di-O-allyl-myo-inositol was regioselectively p-methoxybenzylated at the 3-position to give 1,4-di-O-allyl-3-O-(p-methoxybenzyl)-myo-inositol followed by benzylation of the remaining free hydroxyl groups to give the key intermediate 1,4-di-O-allyl-2,5,6-tri-O-benzyl-3-O-(p-methoxybenzyl)-myo-inositol. Removal of the p-methoxybenzyl and allyl groups gave 2,4,5-tri-O-benzyl-myo-inositol which was phosphitylated with bis(benzyloxy)(diisopropylamino)phosphine to give the fully protected trisphosphite triester. Oxidation using tert-butyl hydroperoxide gave 2,5,6-tri-O-benzyl-1,3,4-tris(dibenzylphospho)-myo-inositol, and deprotection using sodium in liquid ammonia gave racemic myo-inositol 1,3,4-trisphosphate. Deprotection of the key intermediate 1,4-di-O-allyl-2,5,6-tri-O-benzyl-3-O-(p-methoxybenzyl)-myo-inositol by isomerization of allyl groups followed by mild acid hydrolysis gave 2,4,5-tri-O-benzyl-1-O-(p-methoxybenzyl)-myo-inositol, which was converted to the diastereoisomeric (bis-(-)-camphanates. The diastereoisomers were separated by column chromatography and the camphanates and the p-methoxybenzyl group removed by saponification and acid hydrolysis, respectively, for each diastereoisomer to give the enantiomers of 2,4,5-tri-O-benzyl-myo-inositol. The absolute configurations of the latter were established by conversion of 1L-2,5,6-tri-O-benzyl-3-O-(p-methoxybenyl)-myo-inositol to the known 1L-1,2,4,5,6-penta-O-benzyl-myo-inositol. Phosphorylation and deblocking gave the D- and L-enantiomers of myo-inositol 1,3,4-trisphosphate. Biological evaluation in Limulus photoreceptors showed that 1L-myo-inositol 1,3,4-trisphosphate was much more active than the D-enantiomer, producing repetitive bursts of depolarization due to mobilization of intracellular calcium.
Authors:
A M Riley; R Payne; B V Potter
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Publication Detail:
Type:  Journal Article; Research Support, Non-U.S. Gov't    
Journal Detail:
Title:  Journal of medicinal chemistry     Volume:  37     ISSN:  0022-2623     ISO Abbreviation:  J. Med. Chem.     Publication Date:  1994 Nov 
Date Detail:
Created Date:  1994-12-29     Completed Date:  1994-12-29     Revised Date:  2008-11-21    
Medline Journal Info:
Nlm Unique ID:  9716531     Medline TA:  J Med Chem     Country:  UNITED STATES    
Other Details:
Languages:  eng     Pagination:  3918-27     Citation Subset:  IM    
Affiliation:
Department of Medicinal Chemistry, School of Pharmacy and Pharmacology, University of Bath, U.K.
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MeSH Terms
Descriptor/Qualifier:
Animals
Calcium / metabolism*
Horseshoe Crabs
Inositol Phosphates / chemical synthesis,  metabolism*
Photoreceptor Cells, Invertebrate / drug effects*,  metabolism
Stereoisomerism
Chemical
Reg. No./Substance:
0/Inositol Phosphates; 7440-70-2/Calcium; 98102-63-7/inositol 1,3,4-trisphosphate

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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