- Total synthesis of spicamycin
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The first total synthesis of one of the spicamycin congeners, SPM VIII (3), is described. A preliminary model study for construction of the characteristic N-glycoside linkage in spicamycin using tetra-O-benzyl-β-D-mannopyranosylamine (13) and halopurines 5 revealed that Pd-catalyzed conditions successfully provided the coupling products 14 and 15 in good yields. It was also shown that thermal anomerization of the N-glycosides easily occurred, which resulted in the predominant formation of the β-anomer as the thermodynamically favored compound, and the activation energy of anomerization of 15 was estimated to be ca. 30 kcal/mol. The novel aminoheptose unit of spicamycin 6 was prepared stereoselectively by carbon elongation of an acyclic aldehyde, prepared by ring cleavage reaction of a highly functionalized cyclohexane derived from naturally abundant myo-inositol. The Pd-catalyzed coupling reaction of the β-heptopyranosylamine 6 with protected 6-chloropurine 5d, followed by deprotection, provided spicamycin amino nucleoside 2, whose condensation with dodecanoylglycine completed the total synthesis of 3. This study confirmed the proposed unique structure of a novel nucleoside antibiotic.
- Suzuki, Tamotsu,Suzuki, Sayaka T.,Yamada, Iwao,Koashi, Yoshiaki,Yamada, Kazue,Chida, Noritaka
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p. 2874 - 2880
(2007/10/03)
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- Total synthesis of spicamycin amino nucleoside.
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[formula: see text] The first total synthesis of spicamycin amino nucleoside 2 has been achieved. The aminoheptose unit 5 was prepared stereoselectively from myo-inositol, and the characteristic N-glycoside linkage was constructed by way of Pd-catalyzed coupling reaction of 5 with 6-chloropurine derivative 6.
- Suzuki,Tanaka,Yamada,Koashi,Yamada,Chida
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p. 1137 - 1140
(2007/10/03)
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- The absolute configuration and optical purity of (-)- and (+)-1,2:4,5-di-O-cyclohexylidene-myo-inositols
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The absolute configurations of (-)- and (+)-1,2:4,5-di-O-cyclohexylidene-myo-inositols are derived as 1D- and 1L-1,2:4,5-di-O-cyclohexylidene-myo-inositols respectively, and are reverse of the most recent literature assignments.
- Aneja,Aneja,Parra
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- Synthesis and Some Properties of D-myo-Inositol 1,4,5-Tris(dihydrogen phosphate)
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Optically active myo-inositol 1,4,5-tris(dihydrogen phosphate) 1, which has now been recognized as a second messenger in a new intracellular signal transduction system, has been prepared starting from myo-inositol.The key step, phosphorylation of an adequately protected polyhydroxy derivative, was accomplished by three methods, among which a phosphoramidite method using a new phosphitylating agent, o-xylylene N,N-diethylphosphoramidite, gave the triphosphoric ester in quantitative yield.Optical resolution was effectively realized by derivatization into diastereoisomeric l-menthoxyacetic esters.NMR spectra and optical rotation are shown to depend on the pH of an aqueous solution of compound 1.
- Ozaki, Shoichiro,Kondo, Yoshihisa,Shiotani, Naokazu,Ogasawara, Tomio,Watanabe, Yutaka
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p. 729 - 738
(2007/10/02)
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- The synthesis of DL-1-(hexadecanoyloxy)methyl- and 1-O-hexadecanoyl-inositols as potential inhibitors of phospholipase C
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The synthesis of racemic analogues of phosphatidylinositol (PI) and phosphatidylinositol 4,5-bisphosphate (PIP2) starting from myo-inositol is described. Inositol derivatives with and without homologation at C(1) and with and without ionic grou
- James,Massy,Wyss
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p. 1037 - 1057
(2007/10/02)
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- TOTAL SYNTHESIS OF OPTICALLY ACTIVE MYO-INOSITOL 1,4,5-TRIS(PHOSPHATE)
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Optically active myo-inositol 1,4,5-tris(phosphate) has been synthesized starting from myo-inositol.
- Ozaki, Shoichiro,Watanabe, Yutaka,Ogasawara, Tomio,Kondo, Yoshihisa,Shiotani, Naokazu,et al.
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p. 3157 - 3160
(2007/10/02)
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