Synthesis of α-d-Glcp-(1→3)-α-d-Galf-(1→2)-α-l- Rhap constituent of the CPS of Streptococcus pneumoniae 22F. Effect of 3-O-substitution in 1,2-cis α-d-galactofuranosylation
The synthesis of the trisaccharide α-d-Glcp-(1→3)-α-d- Galf-(1→2)-l-Rhap (3) constituent of Streptococcus pneumonia 22F was achieved with complete diastereoselectivity. This is the first example of a synthesis of an internal α-d-Galf containing oligosaccharide of a pathogen microorganism. Allyl α-d-...
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| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_20462069_v4_n7_p3368_Gola |
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todo:paper_20462069_v4_n7_p3368_Gola2023-10-03T16:38:37Z Synthesis of α-d-Glcp-(1→3)-α-d-Galf-(1→2)-α-l- Rhap constituent of the CPS of Streptococcus pneumoniae 22F. Effect of 3-O-substitution in 1,2-cis α-d-galactofuranosylation Gola, G. Gallo-Rodriguez, C. Diastereo-selectivity Novel precursors Orthogonal groups Protecting group Protective group Streptococcus pneumoniae Trichloroacetimidate Stereoselectivity The synthesis of the trisaccharide α-d-Glcp-(1→3)-α-d- Galf-(1→2)-l-Rhap (3) constituent of Streptococcus pneumonia 22F was achieved with complete diastereoselectivity. This is the first example of a synthesis of an internal α-d-Galf containing oligosaccharide of a pathogen microorganism. Allyl α-d-galactofuranoside, used as novel precursor of the internal Galf, allowed the introduction of an orthogonal group at O-3. The trichloroacetimidate method was used for the construction of 1,2-cis-α-d-galactofuranosyl linkage. The influence of the 3-O-substituent (PMB, Bz, PFBz, PMBz, TIPS) was evaluated in benzylated galactofuranosyl trichloroacetimidate donors in terms of yield and selectivity of α-d-Galf-(1→2)-α-l-Rhap product as well as donor rearrangement by-product. Complete stereoselectivity was observed with all protecting groups used in the Galf donor, but the 3-O-benzoyl substitution gave the best yield. Protective groups were also evaluated in the rhamnoside acceptor, benzyl substitution was a requirement for complete stereoselectivity. Fil:Gallo-Rodriguez, C. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_20462069_v4_n7_p3368_Gola |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Diastereo-selectivity Novel precursors Orthogonal groups Protecting group Protective group Streptococcus pneumoniae Trichloroacetimidate Stereoselectivity |
| spellingShingle |
Diastereo-selectivity Novel precursors Orthogonal groups Protecting group Protective group Streptococcus pneumoniae Trichloroacetimidate Stereoselectivity Gola, G. Gallo-Rodriguez, C. Synthesis of α-d-Glcp-(1→3)-α-d-Galf-(1→2)-α-l- Rhap constituent of the CPS of Streptococcus pneumoniae 22F. Effect of 3-O-substitution in 1,2-cis α-d-galactofuranosylation |
| topic_facet |
Diastereo-selectivity Novel precursors Orthogonal groups Protecting group Protective group Streptococcus pneumoniae Trichloroacetimidate Stereoselectivity |
| description |
The synthesis of the trisaccharide α-d-Glcp-(1→3)-α-d- Galf-(1→2)-l-Rhap (3) constituent of Streptococcus pneumonia 22F was achieved with complete diastereoselectivity. This is the first example of a synthesis of an internal α-d-Galf containing oligosaccharide of a pathogen microorganism. Allyl α-d-galactofuranoside, used as novel precursor of the internal Galf, allowed the introduction of an orthogonal group at O-3. The trichloroacetimidate method was used for the construction of 1,2-cis-α-d-galactofuranosyl linkage. The influence of the 3-O-substituent (PMB, Bz, PFBz, PMBz, TIPS) was evaluated in benzylated galactofuranosyl trichloroacetimidate donors in terms of yield and selectivity of α-d-Galf-(1→2)-α-l-Rhap product as well as donor rearrangement by-product. Complete stereoselectivity was observed with all protecting groups used in the Galf donor, but the 3-O-benzoyl substitution gave the best yield. Protective groups were also evaluated in the rhamnoside acceptor, benzyl substitution was a requirement for complete stereoselectivity. |
| format |
JOUR |
| author |
Gola, G. Gallo-Rodriguez, C. |
| author_facet |
Gola, G. Gallo-Rodriguez, C. |
| author_sort |
Gola, G. |
| title |
Synthesis of α-d-Glcp-(1→3)-α-d-Galf-(1→2)-α-l- Rhap constituent of the CPS of Streptococcus pneumoniae 22F. Effect of 3-O-substitution in 1,2-cis α-d-galactofuranosylation |
| title_short |
Synthesis of α-d-Glcp-(1→3)-α-d-Galf-(1→2)-α-l- Rhap constituent of the CPS of Streptococcus pneumoniae 22F. Effect of 3-O-substitution in 1,2-cis α-d-galactofuranosylation |
| title_full |
Synthesis of α-d-Glcp-(1→3)-α-d-Galf-(1→2)-α-l- Rhap constituent of the CPS of Streptococcus pneumoniae 22F. Effect of 3-O-substitution in 1,2-cis α-d-galactofuranosylation |
| title_fullStr |
Synthesis of α-d-Glcp-(1→3)-α-d-Galf-(1→2)-α-l- Rhap constituent of the CPS of Streptococcus pneumoniae 22F. Effect of 3-O-substitution in 1,2-cis α-d-galactofuranosylation |
| title_full_unstemmed |
Synthesis of α-d-Glcp-(1→3)-α-d-Galf-(1→2)-α-l- Rhap constituent of the CPS of Streptococcus pneumoniae 22F. Effect of 3-O-substitution in 1,2-cis α-d-galactofuranosylation |
| title_sort |
synthesis of α-d-glcp-(1→3)-α-d-galf-(1→2)-α-l- rhap constituent of the cps of streptococcus pneumoniae 22f. effect of 3-o-substitution in 1,2-cis α-d-galactofuranosylation |
| url |
http://hdl.handle.net/20.500.12110/paper_20462069_v4_n7_p3368_Gola |
| work_keys_str_mv |
AT golag synthesisofadglcp13adgalf12alrhapconstituentofthecpsofstreptococcuspneumoniae22feffectof3osubstitutionin12cisadgalactofuranosylation AT gallorodriguezc synthesisofadglcp13adgalf12alrhapconstituentofthecpsofstreptococcuspneumoniae22feffectof3osubstitutionin12cisadgalactofuranosylation |
| _version_ |
1782025798470860800 |