Details
| Original language | English |
|---|---|
| Pages (from-to) | 2717-2729 |
| Number of pages | 13 |
| Journal | Chemistry - A European Journal |
| Volume | 8 |
| Issue number | 12 |
| Publication status | Published - 10 Jun 2002 |
Abstract
The preparation of novel cyclic 1,4-butanediol-linked oligoaminodeoxysugars 3-5 and 7 is described which are potential binders to polynucleotides. Neooligosaccharides 3-5 are assembled by two consecutive metathesis protocols. In the first phase metathesis-mediated dimerization of an aminodeoxymonosaccharide which was either allylated at the anomeric center or at C4 led to E/Z mixtures of C2-symmetric homodimers which were transformed into the corresponding 1,4-butanediol linked disaccharides by catalytic hydrogenation of the central olefinic double bond. Double O-allylation of the head-to-head dimer set the stage for macrocyclization by means of ringclosing metathesis. This ring-closing process was highly dependent of the configuration in the carbohydrate moieties. arabino-Configured homodimer 15 directly yielded the macrocycle 32 which contains two sugar units while under the same metathesis conditions the corresponding ribo-configured starting homodimer 19 afforded cyclic neotetra- and neohexasaccharides 34 and 35 after a preceding dimerization and trimerization step, respectively. In addition, homodimer 23 was coupled with silylglycoside 14a under Lewis-acid promoted glycosidation conditions to furnish the doubly glycosylated homodimer 31. Ring-closing metathesis afforded the macrocyclic neoaminodeoxyoligosaccharide 36 with alternating 1,4-butanediol linkage and glycosidic bond. The primary cyclization products were finally transformed into the respective cyclic neoaminodeoxyoligosaccharides 3-5 and 7 by catalytic hydrogenation and standard deprotection conditions.
Keywords
- Antibiotics, Carbohydrates, Glycosidation, Macrocycles, Metathesis
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- Organic Chemistry
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In: Chemistry - A European Journal, Vol. 8, No. 12, 10.06.2002, p. 2717-2729.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - First preparation of spacer-linked cyclic neooligoaminodeoxysaccharides
AU - Chen, Guang Wu
AU - Kirschning, Andreas
PY - 2002/6/10
Y1 - 2002/6/10
N2 - The preparation of novel cyclic 1,4-butanediol-linked oligoaminodeoxysugars 3-5 and 7 is described which are potential binders to polynucleotides. Neooligosaccharides 3-5 are assembled by two consecutive metathesis protocols. In the first phase metathesis-mediated dimerization of an aminodeoxymonosaccharide which was either allylated at the anomeric center or at C4 led to E/Z mixtures of C2-symmetric homodimers which were transformed into the corresponding 1,4-butanediol linked disaccharides by catalytic hydrogenation of the central olefinic double bond. Double O-allylation of the head-to-head dimer set the stage for macrocyclization by means of ringclosing metathesis. This ring-closing process was highly dependent of the configuration in the carbohydrate moieties. arabino-Configured homodimer 15 directly yielded the macrocycle 32 which contains two sugar units while under the same metathesis conditions the corresponding ribo-configured starting homodimer 19 afforded cyclic neotetra- and neohexasaccharides 34 and 35 after a preceding dimerization and trimerization step, respectively. In addition, homodimer 23 was coupled with silylglycoside 14a under Lewis-acid promoted glycosidation conditions to furnish the doubly glycosylated homodimer 31. Ring-closing metathesis afforded the macrocyclic neoaminodeoxyoligosaccharide 36 with alternating 1,4-butanediol linkage and glycosidic bond. The primary cyclization products were finally transformed into the respective cyclic neoaminodeoxyoligosaccharides 3-5 and 7 by catalytic hydrogenation and standard deprotection conditions.
AB - The preparation of novel cyclic 1,4-butanediol-linked oligoaminodeoxysugars 3-5 and 7 is described which are potential binders to polynucleotides. Neooligosaccharides 3-5 are assembled by two consecutive metathesis protocols. In the first phase metathesis-mediated dimerization of an aminodeoxymonosaccharide which was either allylated at the anomeric center or at C4 led to E/Z mixtures of C2-symmetric homodimers which were transformed into the corresponding 1,4-butanediol linked disaccharides by catalytic hydrogenation of the central olefinic double bond. Double O-allylation of the head-to-head dimer set the stage for macrocyclization by means of ringclosing metathesis. This ring-closing process was highly dependent of the configuration in the carbohydrate moieties. arabino-Configured homodimer 15 directly yielded the macrocycle 32 which contains two sugar units while under the same metathesis conditions the corresponding ribo-configured starting homodimer 19 afforded cyclic neotetra- and neohexasaccharides 34 and 35 after a preceding dimerization and trimerization step, respectively. In addition, homodimer 23 was coupled with silylglycoside 14a under Lewis-acid promoted glycosidation conditions to furnish the doubly glycosylated homodimer 31. Ring-closing metathesis afforded the macrocyclic neoaminodeoxyoligosaccharide 36 with alternating 1,4-butanediol linkage and glycosidic bond. The primary cyclization products were finally transformed into the respective cyclic neoaminodeoxyoligosaccharides 3-5 and 7 by catalytic hydrogenation and standard deprotection conditions.
KW - Antibiotics
KW - Carbohydrates
KW - Glycosidation
KW - Macrocycles
KW - Metathesis
UR - http://www.scopus.com/inward/record.url?scp=0037124568&partnerID=8YFLogxK
U2 - 10.1002/1521-3765(20020617)8:12<2717::AID-CHEM2717>3.0.CO;2-P
DO - 10.1002/1521-3765(20020617)8:12<2717::AID-CHEM2717>3.0.CO;2-P
M3 - Article
C2 - 12391650
AN - SCOPUS:0037124568
VL - 8
SP - 2717
EP - 2729
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 12
ER -