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Scheme 5. Access to precursors of CS-D (35) andchondroitin sulfates
K, L, andM ( 36). Reagents and conditions: a) PhCOCN, pyridine,
room temperature, 6 h, 80%; b) (ClAc)2O, pyridine, 08C, 1 h, 95%;
c) 75% AcOH, 1008C, 20 min; then (ClAc)2O, pyridine, CH2Cl2,
ꢁ208C, 30 min, 72%; d) PhCOCl, pyridine, 08C, 1 h, 91%; e) Bu2SnO,
dioxane/benzene, reflux, 7 h; then PhCOCl, room temperature, 8 h,
68%.
In conclusion, 1 can be readily prepared on a multigram
scale and its versatility has been demonstrated. This short-
ened sequence renders this approach very attractive and
competitive for the preparation of size-defined chondroitin
oligomers. Also relevant is the rapid access to precursors for
the preparation of various sulfo forms starting from the
common intermediate 25. This route can also be applied to
other biologically important members of the glycosaminogly-
can family such as dermatan sulfate and hyaluronic acid. The
synthesis of a collection of chondroitin oligomers and their
various sulfo forms based on this approach is underway, and
will be reported elsewhere in due course.
Received: October 6, 2005
Revised: November 12, 2005
Published online: March 13, 2006
Keywords: carbohydrates · glycosaminoglycans ·
.
oligosaccharides · synthesis design
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