Synthetic Aspects of Aminodeoxy Sugars of Antibiotics

Pelyvás, István F.; Monneret, Claude; Herczegh, Pál

doi:10.1007/978-3-642-73399-4

Cited by 33 publications

(14 citation statements)

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“…The 1,3‐polyol systems prepared from the enzymatic reaction could serve as useful synthons 5–8. An example is the stereoselective C2 alkylation of β ‐hydroxylactone with an alkyl bromide under chelation control directed by the β ‐hydroxy group (Scheme ) 9.…”

Section: Methodsmentioning

confidence: 99%

Aldolase-Catalyzed Asymmetric Synthesis of Novel Pyranose Synthons as a New Entry to Heterocycles and Epothilones

Liu

Wong

2002

Angewandte Chemie International Edition

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Section: Methodsmentioning

confidence: 99%

Aldolase-Catalyzed Asymmetric Synthesis of Novel Pyranose Synthons as a New Entry to Heterocycles and Epothilones

Liu

Wong

2002

Angewandte Chemie International Edition

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“…1 (15 mL)] at -78°C were added to a solution of 5 (0.150 g, 0.411 mmol) in THF (30 mL) also at -78°C. The resulting solution was stirred for 1.5 h, and then a solution of phenylselenyl bromide (0.174 g, 0.74 mmol) in THF (15 mL) was added dropwise via cannula.…”

Section: Conversion Of 15 To Primary Amine 16mentioning

confidence: 99%

“…6-Deoxy-3-aminohexoses are the most common of the aminosugars, and these have been the focus of substantial synthetic effort. 1 6-Deoxy-4-aminohexoses are considerably less common, and as a consequence, synthetic approaches to these have been less developed. Biologically active members of the latter class include: ossamine 1, the aminosugar fragment from the fungal metabolite ossamycin; 2 methyl-L-kedarosaminide 2, from the ene-diyne antitumor agent kedarcin; 3 callepeltose 3, from the antitumor cyclodepsipeptide callipeltose; 4 and the aminosugar moiety of antibiotic C-1027 4 ( Figure 1).…”

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confidence: 99%

“…Commercially available reagents were used as received except as indicated. 1 H NMR (JS-300, 300 MHz), 13 Lactol Acetates 7a, b DIBAL-H (0.87 mL, 0.866 mmol, 1 M in hexanes) was added to a solution of 6 (0.220 g, 0.577 mmol) in anhyd toluene (12 mL) at -78°C. After stirring for 2.5 h, acetic anhydride (0.22 mL) and pyridine (0.14 mL) were added followed by a solution of DMAP (0.10 g, 0.808 mmol) in toluene (5 mL …”

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confidence: 99%

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Synthesis of 6-Deoxy-4-aminohexoses from Cyclopentanones

Heileman¹,

Hegedus²

2001

Synthesis

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Procedures for the conversion of (±)-2-methoxy-2-methyl-3-oxazolidinylcyclopentanone into a variety of 4-amino-6-deoxyhexoses have been developed. These involve Baeyer-Villiger ring expansions, reductive methylations and epimerizations.Keywords: (±)-2-methoxy-2-methyl-3-oxazolidinylcyclopentanone, 4-amino-6-deoxyhexoses, Baeyer-Villiger ring expansions, reductive methylation, epimerizations 6-Deoxyaminohexoses are common aminosugar fragments found in many antibiotic and antitumor agents, as well as in the cell walls of many bacteria. 6-Deoxy-3-aminohexoses are the most common of the aminosugars, and these have been the focus of substantial synthetic effort. 1 6-Deoxy-4-aminohexoses are considerably less common, and as a consequence, synthetic approaches to these have been less developed. Biologically active members of the latter class include: ossamine 1, the aminosugar fragment from the fungal metabolite ossamycin; 2 methyl-L-kedarosaminide 2, from the ene-diyne antitumor agent kedarcin; 3 callepeltose 3, from the antitumor cyclodepsipeptide callipeltose; 4 and the aminosugar moiety of antibiotic C-1027 4 ( Figure 1). 5 Synthetic precursors to these 6-deoxy-4-aminohexoses include compounds from the "chiral pool" such as threonine, 3c,d,6a ethyl lactate, 3e rhammose, 4,7 glucose, 2,3b and less commonly from precursors synthesized asymmetrically. 5,8 Recent research in these laboratories has been directed toward the utilization of chiral cyclobutanones, produced by the photochemical reaction between chromium carbene complexes and chiral ene carbamates, 9 as precursors to biologically active compounds via ring expansion procedures. These include 4-disubstituted butenolides, 10 4-disubstituted nucleoside analogs, 11 carbacyclic nucleoside analogs, 12 and aminocyclopentitols. 13 The development of synthetic approaches to 5-methoxy analogs of 4-amino-6-deoxyhexoses are described below.The key starting material for these studies, cyclopentanone 5, was available in two steps and 60-70% overall yield by the diazomethane ring expansion 14 of the photochemically generated 2-methoxy-2-methylcyclobutanone. Treatment with m-CPBA resulted in clean Baeyer-Villiger rearrangement 10a with exclusive migration of the more-hindered terminus with complete retention of configuration to produce lactone 6 in excellent yield (Scheme 1). This lactone was quite sensitive to acidcatalyzed epimerization at the anomeric (ketal) carbon and required removal of all traces of m-chlorobenzoic acid (aqueous NaHCO 3 ) followed by immediate purification by flash chromatography.Conventional DIBAL-H reduction of the lactone to the lactol resulted in ring opening because of the methoxide leaving group. However, quenching the low temperature DIBAL-H reduction with acetic anhydride in the presence of pyridine and DMAP 15 produced lactol acetate 7 in excellent yield as a 1:1 mixture of diastereoisomers at the acetate-bearing center. Treatment of this mixture with BF 3 etherate in methanol cleanly exchanged the acetate for a methoxy group giving 8 again as ...

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“…The book Synthetic aspects of aminodeoxy sugars of antibiotics by I.F. Pelyvas, C. Monneret and P. Herczegh [19], published in 1988, with its meticulous discussion of details, has provided an invaluable landmark in this respect. A decade later, L.A. Otsomaa and A.M.P.…”

Section: Introductionmentioning

confidence: 98%