Direct Synthesis of Pseudo-Disaccharides by Rearrangement of Unsaturated Disaccharides

Site-selective hexa-hetero-functionalization of α-cyclodextrin an archetypical C6-symmetric concave cycle

“…For some time now we have been developing methods to hetero-functionalize CDs based on the understanding of the mechanism of a deprotection reaction. This reaction is a ARTICLE debenzylation reaction discovered serendipitously 45,46 and operated by diisobutylaluminium hydride (DIBAL-H) leading to CD A,D-diol 3 from perbenzylated CD 1 (ref. 47).…”

Site-selective hexa-hetero-functionalization of α-cyclodextrin an archetypical C6-symmetric concave cycle

“…For some time now we have been developing methods to hetero-functionalize CDs based on the understanding of the mechanism of a deprotection reaction. This reaction is a ARTICLE debenzylation reaction discovered serendipitously 45,46 and operated by diisobutylaluminium hydride (DIBAL-H) leading to CD A,D-diol 3 from perbenzylated CD 1 (ref. 47).…”

Synthesis of carbasugar-containing non-glycosidically linked pseudodisaccharides and higher pseudooligosaccharides

“…Hence, disaccharides were modified to give exo-glycals (277), which rearranged upon treatment with TIBAL to give pseudodisaccharides (278) (Scheme 12). 80 The reaction worked well for a range of (1?6)-or (1?4)-linked compounds, but debenzylation was a competing reaction when the anomeric substituent was an a-methyl glucoside (278a,b). The reaction was diastereoselective and the products with an axial C-1 orientation were formed.…”

Design and synthesis of glycomimetics: Recent advances

“…Intramolecular aldol condensation ensues, affording the carbacycle 18 . The method has been strongly improved replacing HgCl 2 with AlBu 3 (TIBAL) or Ti(O i Pr)Cl 3 which, upon coordination of the anomeric and the C‐2 oxygens, allows the rearrangement to proceed while maintaining the glycosidic bond …”

Site-selective hexa-hetero-functionalization of α-cyclodextrin an archetypical C6-symmetric concave cycle

“…For some time now we have been developing methods to hetero-functionalize CDs based on the understanding of the mechanism of a deprotection reaction. This reaction is a ARTICLE debenzylation reaction discovered serendipitously 45,46 and operated by diisobutylaluminium hydride (DIBAL-H) leading to CD A,D-diol 3 from perbenzylated CD 1 (ref. 47).…”

Synthesis of carbasugar-containing non-glycosidically linked pseudodisaccharides and higher pseudooligosaccharides

“…Hence, disaccharides were modified to give exo-glycals (277), which rearranged upon treatment with TIBAL to give pseudodisaccharides (278) (Scheme 12). 80 The reaction worked well for a range of (1?6)-or (1?4)-linked compounds, but debenzylation was a competing reaction when the anomeric substituent was an a-methyl glucoside (278a,b). The reaction was diastereoselective and the products with an axial C-1 orientation were formed.…”

Design and synthesis of glycomimetics: Recent advances

“…Intramolecular aldol condensation ensues, affording the carbacycle 18 . The method has been strongly improved replacing HgCl 2 with AlBu 3 (TIBAL) or Ti(O i Pr)Cl 3 which, upon coordination of the anomeric and the C‐2 oxygens, allows the rearrangement to proceed while maintaining the glycosidic bond …”

Site-selective hexa-hetero-functionalization of α-cyclodextrin an archetypical C6-symmetric concave cycle

“…For some time now we have been developing methods to hetero-functionalize CDs based on the understanding of the mechanism of a deprotection reaction. This reaction is a ARTICLE debenzylation reaction discovered serendipitously 45,46 and operated by diisobutylaluminium hydride (DIBAL-H) leading to CD A,D-diol 3 from perbenzylated CD 1 (ref. 47).…”

Synthesis of carbasugar-containing non-glycosidically linked pseudodisaccharides and higher pseudooligosaccharides

“…Hence, disaccharides were modified to give exo-glycals (277), which rearranged upon treatment with TIBAL to give pseudodisaccharides (278) (Scheme 12). 80 The reaction worked well for a range of (1?6)-or (1?4)-linked compounds, but debenzylation was a competing reaction when the anomeric substituent was an a-methyl glucoside (278a,b). The reaction was diastereoselective and the products with an axial C-1 orientation were formed.…”

Design and synthesis of glycomimetics: Recent advances

“…Intramolecular aldol condensation ensues, affording the carbacycle 18 . The method has been strongly improved replacing HgCl 2 with AlBu 3 (TIBAL) or Ti(O i Pr)Cl 3 which, upon coordination of the anomeric and the C‐2 oxygens, allows the rearrangement to proceed while maintaining the glycosidic bond …”