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was carried out at 80 8C overnight. The reaction mixture
was filtered and the filtrate was then poured into dichloro-
methane (100 mL) followed by washing with water
(150 mL) four times. The organic phase was dried over
anhydrous sodium sulfate and concentrated under reduced
pressure to give a yellow oil (3.31 g, 90.1%).
phase was extracted with dichloromethane (10 mL) three
times. The organic phases were combined and washed in
order with water (50 mL), saturated aqueous sodium bicar-
bonate (50 mL), water (50 mL), and dried over anhydrous
magnesium sulfate. The filtrate was concentrated and puri-
fied by silica gel chromatography (40% ethyl acetate in hex-
ane, Rf 5 0.5) to give a gel-like product (0.89 g, 81.3%).
1H NMR (300 MHz, CDCl3): d (ppm) 1.42 (m, 2H) 1.64 (m,
4H) 2.33 (t, J 5 7.4 Hz, 2H) 3.28 (t, J 5 6.9 Hz, 2H) 3.68 (s,
3H). 13C NMR (75 MHz, CDCl3), d (ppm): 24.17 (s), 25.97
(s), 28.27 (s), 33.52 (s), 50.94 (s), 51.35 (s), 173.53 (s).
1H NMR (300 MHz, CDCl3), d (ppm): 2.00 (s, 3H), 2.05 (s,
3H), 2.10 (s, 3H), 2.16 (s, 3H), 3.75–3.95 (m, 2H), 4.00–4.13
(m, 2H), 4.24–4.30 (m, 1H), 4.36 (t, J 5 4.50 Hz, 2H), 4.87 (s,
1H), 5.25–5.38 (m, 3H), 5.88 (dd, J 5 10.50, 1.50, 1H), 6.16
(q, J 5 9.00, 1H), 6.45 (d, J 5 18.00, 1H). 13C NMR (75 MHz,
CDCl3), d (ppm): 20.48 (s), 20.52 (s), 20.57 (s), 20.67 (s),
59.49 (s), 61.99 (s), 62.32 (s), 62.85 (s), 63.10 (s), 65.47 (s),
65.75 (s), 65.91 (s), 66.04 (s), 68.23 (s), 68.59 (s), 68.62 (s),
68.78 (s), 68.81 (s), 69.33 (s), 70.50 (s), 90.49 (s), 97.53 (s),
127.91 (s), 131.16 (s), 165.70 (s), 167.84 (s), 169.52 (s),
169.64 (s), 169.79 (s), 170.40 (s).
Synthesis of Azide Functionalized Diol (5)
In a round-bottom flask, methyl 6-azidohexanoate (2.2 g,
12.8 mmol) and diethanolamine (2.75 g, 26.2 mmol) were
added. Then the mixture was stirred at 80 8C overnight. The
product was purified by column chromatography (10% ethyl
acetate in hexane, Rf 5 0.5) to give a slightly yellow oil
(1.61 g, 51.4%).
1H NMR (300 MHz, CDCl3), d (ppm): 1.40–1.48 (m, 2H),
1.59–1.74 (m, 4H), 2.43 (t, J 5 7.50 Hz, 2H), 3.29 (t, J 5 7.50
Hz, 2H), 3.38 (br, 2H), 3.51 (t, J 5 4.50 Hz, 4H), 3.56 (t,
J 5 4.50 Hz, 4H), 3.79 (t, J 5 6.00 Hz, 4H), 3.86 (t, J 5 6.00
Hz, 4H). 13C NMR (75 MHz, CDCl3), d (ppm): 24.57 (s), 26.32
(s), 28.55 (s), 33.13 (s), 50.32 (s), 51.13 (s), 51.96 (s), 60.42
(s), 60.99 (s), 174.92 (s).
Synthesis of Acetyl Protected Propargyl
a-D-Mannopyranoside
To a solution of acetyl protected mannose (0.50 g, 1.28
mmol) in dry dichloromethane (10 mL), boron trifluoride
etherate (0.73 g, 5.12 mmol) was added dropwise in ice bath
under nitrogen. The mixture was allowed to warm to room
temperature and stirred for 2 h. Propargyl alcohol (0.29 g,
5.12 mmol) was then added and the mixture was stirred at
room temperature for 24 h. The mixture was washed succes-
sively with water (20 mL), saturated aqueous sodium bicar-
bonate (20 mL), water (20 mL), and dried over anhydrous
magnesium sulfate. The filtrate was concentrated and puri-
fied by silica gel chromatography (20% ethyl acetate in hex-
ane, Rf 5 0.3) to give a white solid (0.34 g, 64.7%).
Synthesis of Acetyl Protected Mannose (1)
Two drops of concentrated sulfuric acid was added to a
stirred mixture of acetic anhydride (29.21 g, 0.278 mol) and
D(1)-mannose (4.98 g, 27.8 mmol) at 0 8C. The mixture was
stirred for 10 min at 0 8C and then allowed to warm up to
room temperature and stirred for a further 30 min. Then,
the mixture was diluted with ice water (100 mL) and
extracted with ethyl acetate (100 mL). The extract was
washed with water (100 mL) three times and then saturated
aqueous sodium bicarbonate (100 mL). The organic phase
was dried over anhydrous magnesium sulfate and concen-
trated under reduced pressure to yield a colorless gel-like
product (8.68 g, 80.4%).
1H NMR (300 MHz, CDCl3), d (ppm): 2.00 (s, 3H), 2.05 (s,
3H), 2.12 (s, 3H), 2.17 (s, 3H), 2.48 (t, J 5 3.00 Hz, 1H),
4.10–4.15 (m, 2H), 4.27–4.33 (m, 3H), 5.05 (s, 1H), 5.28–
5.30 (m, 1H), 5.34–5.37 (m, 2H). 13C NMR (75 MHz, CDCl3),
d (ppm): 20.52 (s), 20.55 (s), 20.60 (s), 20.72 (s), 54.86 (s),
62.26 (s), 65.99 (s), 68.85 (s), 68.94 (s), 69.29 (s), 75.51 (s),
77.87 (s), 96.18 (s), 169.54 (s), 169.66 (s), 169.77 (s),
170.44 (s).
1H NMR (300 MHz, CDCl3), d (ppm): 1.96–2.18 (m, 15H),
3.76–4.12 (m, 2H), 4.21–4.29 (m, 1H), 5.08–5.21 (m, 1H),
5.26–5.44 (m, 2H), 5.83–6.04 (m, 1H). 13C NMR (75 MHz,
CDCl3), d (ppm): 20.50 (s), 62.00 (s), 65.44 (s), 68.20 (s),
68.64 (s), 70.48 (s), 90.49 (s), 167.90 (s), 169.38 (s), 169.56
(s), 169.80 (s), 170.45 (s).
Synthesis of Azide Functionalized Polyester (pN3)
In a round-bottom flask, azide functionalized diol (1.614 g,
6.61 mmol), succinic acid (0.781 g, 6.61 mmol), and DPTS
(0.7728 g, 2.64 mmol) were added. The flask was evacuated
and backfilled with nitrogen three times. Anhydrous
dichloromethane (6.6 mL) was added to the flask and the
mixture was cooled in an ice bath. DIC (2.50 g, 19.83 mmol)
was added dropwise and the reaction was carried out at
room temperature for 48 h. The polymer was purified by
precipitation in methanol.
Synthesis of Acetyl Protected Mannose Based
Acrylate (2)
In a round-bottom flask, acetyl protected mannose (1.00 g,
5.56 mmol), 2-hydroxyethyl acrylate (1.29 g, 11.11 mmol),
and anhydrous dichloromethane (11 mL) were added. The
flask was placed in an ice bath and boron trifluoride ether-
ate (1.57 g, 11.11 mmol) was added dropwise over 20 min.
The flask was kept in an ice bath for an hour and then the
reaction continued at room temperature for 24 h. The mix-
ture was then poured into 15 mL ice water and the aqueous
1H NMR (300 MHz, CDCl3), d (ppm): 1.38–1.48 (m, 2H),
1.62–1.73 (m, 4H), 2.38 (t, J 5 7.50 Hz, 2H), 2.63 (m, 4H),
3.30 (t, J 5 7.50 Hz, 2H), 3.63 (m, 4H), 4.24 (m, 4H).
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