M. L. Lepage, A. Bodlenner, P. Compain
FULL PAPER
IR (neat): ν = 3468 (broad, O–H), 2111 (N ) cm–1. HRMS (ESI): IR (neat): ν = 3453 (broad, O–H), 2109 (N ) cm–1. HRMS (ESI):
˜
˜
3
3
m/z calcd. for C27H29O5N3 [M + Na]+ 498.200; found 498.197.
m/z calcd. for C20H23O4N3 [M + Na]+ 392.158; found 392.158.
Compound 19β: Rf = 0.35 (EtOAc/PE, 3:7). [α]2D3 = –73.2 (c = 1,
CHCl3). 1H NMR (300 MHz, CDCl3): δ = 7.47–7.24 (m, 15 H,
ArH), 4.93 (d, J = 11.0 Hz, 1 H, OCH2Ph), 4.93 (d, J = 11.6 Hz,
1 H, OCH2Ph), 4.84 (d, J = 11.6 Hz, 1 H, OCH2Ph), 4.67 (d, J =
11.0 Hz, 1 H, OCH2Ph), 4.65 (s, 2 H, OCH2Ph), 4.45 (s, 1 H, 1-
H), 3.98 (dd, J = 9.7, 9.5 Hz, 1 H, 4-H), 3.97–3.85 (m, 2 H, 2-H
and 6-Ha), 3.78 (m, 1 H, 6-Hb), 3.57 (dd, J = 9.5, 2.7 Hz, 1 H, 3-
H), 3.42 (ddd, J = 9.7, 5.0, 2.7 Hz, 1 H, 5-H), 2.06 (br. s, 1 H,
OH) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 138.1, 138.03,
137.99, 128.64 (2), 128.61 (2), 128.43 (2), 128.37 (2), 128.27 (2),
128.04, 127.99, 127.93, 127.7 (2), 86.8, 82.8, 78.2, 76.0, 75.5, 74.9,
1-Azido-3,4-di-O-benzyl- -mannopyranoses (23): Compound 22 was
treated as described in the general procedure and the reaction mix-
ture was stirred for 15 min at room temp. (conditions A).
D
Compound 23α: Rf = 0.18 (EtOAc/PE, 2:3). [α]2D3 = +175.7 (c = 0.5,
CHCl3). 1H NMR (300 MHz, CDCl3): δ = 7.39–7.27 (m, 10 H,
ArH), 5.41 (d, J = 1.8 Hz, 1 H, 1-H), 4.88 (d, J = 10.9 Hz, 1 H,
OCH2Ph), 4.71 (d, J = 11.3 Hz, 1 H, OCH2Ph), 4.69 (d, J =
10.9 Hz, 1 H, OCH2Ph), 4.66 (d, J = 11.3 Hz, 1 H, OCH2Ph), 3.98–
3.74 (m, 6 H, 2-H, 3-H, 4-H, 5-H, 6-H), 3.05 (s, 1 H, O2-H), 2.43
(br. s, 1 H, O6-H) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 138.2,
137.6, 128.8 (2), 128.6 (2), 128.3, 128.1 (2), 128.04 (2), 127.99, 89.3,
74.2, 72.5, 62.3 ppm. IR (neat): ν = 3455 (broad, O–H), 2113
˜
79.1, 75.4, 74.0, 73.4, 72.5, 68.5, 61.7 ppm. IR (neat): ν = 3414
˜
(N3) cm–1. HRMS (ESI): m/z calcd. for C27H29O5N3 [M + Na]+
(broad, O–H), 2113 (N3) cm–1. HRMS (ESI): m/z calcd. for
498.200; found 498.197.
C20H23O5N3 [M + Na]+ 408.153; found 408.150.
1,6-Anhydro-2-deoxy-3,4-di-O-benzyl-D-glucopyranose (20): To a
Compound 23β: Rf = 0.36 (EtOAc/PE, 3:7). [α]2D3 = –33.6 (c = 0.5,
CHCl3). 1H NMR (300 MHz, CDCl3): δ = 7.43–7.22 (m, 10 H,
ArH), 4.91 (d, J = 11.0 Hz, 1 H, OCH2Ph), 4.74 (d, J = 11.8 Hz,
1 H, OCH2Ph), 4.69 (d, J = 11.8 Hz, 1 H, OCH2Ph), 4.68 (d, J =
11.0 Hz, 1 H, OCH2Ph), 4.56 (s, 1 H, 1-H), 4.05 (d, J = 3.1 Hz, 1
H, 2-H), 3.98–3.86 (m, 2 H, 4-H, 6-Ha), 3.79 (dd, J = 12.0, 4.0 Hz,
1 H, 6-Hb), 3.60 (dd, J = 9.2, 3.1 Hz, 1 H, 3-H), 3.41 (ddd, J =
9.2, 4.2, 2.6 Hz, 1 H, 5-H), 2.78 (br. s, 1 H, O2-H), 2.33 (br. s, 1
H, O6-H) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 138.1, 137.5,
128.8 (2), 128.6 (2), 128.3, 128.2 (2), 128.1, 128.0 (2), 87.2, 81.5,
stirred solution of 22 (276.6 mg, 808 μmol) in anhydrous CH2Cl2
(1.4 mL) at –10 °C under an atmosphere of argon was added drop-
wise a solution of trifluoromethanesulfonic anhydride (1.0 m in
CH2Cl2, 1.61 mL, 1.61 mmol) and anhydrous pyridine (163 μL,
2.02 mmol) in anhydrous CH2Cl2 (6.1 mL). The addition was per-
formed over 6 min, then the mixture was stirred for 1 h at –10 °C.
The reaction was quenched with cold sat. NaHCO3 (25 mL) and
CH2Cl2 (20 mL) was added. The organic phase was washed with
water (2ϫ 25 mL), dried with Na2SO4, filtered, concentrated to
dryness and further dried under vacuum. The crude mixture was
then diluted with toluene (5 mL) under an atmosphere of argon,
tetrabutylammonium tetrahydroborate (631 mg, 2.45 mmol) was
added and the mixture was stirred at room temp. for 2.25 h. HCl
solution (1.0 m, 15 mL) was carefully added until gas release had
ceased, then the aqueous mixture was extracted with CH2Cl2 (3ϫ
30 mL). The combined organic phases were washed with water and
brine (25 mL each), dried with Na2SO4, filtered and concentrated
to dryness. The crude residue was purified by flash chromatography
(EtOAc/PE, 1:4 to 2:3) to afford 20 (206.8 mg, 78%) as a colourless
oil. Analytical data of 20 matched those reported.[16]
77.8, 75.5, 73.4, 72.1, 69.2, 61.9 ppm. IR (neat): ν = 3428, 2114
˜
(N3) cm–1. HRMS (ESI): m/z calcd. for C20H23O5N3 [M + Na]+
408.153; found 408.150.
Compound 24: To a solution of 9α (208.6 mg, 389 μmol) and 26
(258.8 mg, 515 μmol) in THF (1 mL) was added a bright orange-
yellow suspension of CuSO4·5H2O (49 mg, 195 μmol), sodium as-
corbate (77 mg, 389 μmol) and Na2CO3 (21 mg, 195 μmol) in water
(1 mL). The biphasic mixture was vigorously stirred for 16 h at
room temperature, then EtOAc (50 mL) was added and the organic
phase was washed with water (3ϫ 25 mL). The solvents were evap-
orated and the residue was dissolved in a mixture of CH3CN/H2O/
NH4OH (15:0.5:0.5) and filtered through a pad of silica gel. After
concentration of the filtrate, the crude product was purified by
flash chromatography (EtOAc/PE, 1:4 to 1:1) to afford pure 24
(278.2 mg, 69%) as a viscous colourless oil. Rf = 0.40 (EtOAc/PE,
1:1). [α]2D4 = +55.6 (c = 1, CHCl3). 1H NMR (400 MHz, CDCl3): δ
= 7.61 (s, 1 H, 8-H), 7.37–7.22 (m, 15 H, ArH), 6.19 (d, J = 5.8 Hz,
1 H, 1-H), 4.98 (d, J = 11.0 Hz, 1 H, OCH2Ph), 4.83 (d, J =
10.8 Hz, 1 H, OCH2Ph), 4.82 (d, J = 11.0 Hz, 1 H, OCH2Ph), 4.78
(d, J = 12.2 Hz, 1 H, OCH2Ph), 4.69 (d, J = 12.6 Hz, 1 H,
OCH2CϵC), 4.65 (d, J = 12.2 Hz, 1 H, OCH2Ph), 4.62 (d, J =
12.6 Hz, 1 H, OCH2CϵC), 4.60 (d, J = 3.5 Hz, 1 H, 1Ј-H), 4.58
(d, J = 16.4 Hz, 1 H, OCH2CϵC), 4.54 (d, J = 10.8 Hz, 1 H,
OCH2Ph), 4.53 (t, J = 9.3 Hz, 1 H, 3-H), 4.46 (d, J = 16.4 Hz, 1
H, OCH2CϵC), 4.41 (d, J = 15.8 Hz, 1 H, OCH2CϵC), 4.36 (d, J
= 15.8 Hz, 1 H, OCH2CϵC), 4.22 (d, J = 16.6 Hz, 1 H, 7-Ha),
4.14 (d, J = 16.6 Hz, 1 H, 7-Hb), 4.04 (dd, J = 9.3, 5.8 Hz, 1 H, 2-
1-Azido-2-deoxy-3,4-di-O-benzyl-D-glucopyranoses (21): Compound
22 was treated as described in the general procedure and the reac-
tion mixture was stirred for 3 h40 at room temp. (conditions A).
Compound 21α: Rf = 0.36 (toluene/acetone, 9:1). [α]2D0 = +218.2 (c
1
= 0.5, CHCl3). H NMR (300 MHz, CDCl3): δ = 7.40–7.23 (m, 10
H, ArH), 5.49 (dd, J = 3.2, J = 1.5 Hz, 1 H, 1-H), 4.95 (d, J =
11.1 Hz, 1 H, OCH2Ph), 4.70 (d, J = 11.1 Hz, 1 H, OCH2Ph), 4.66
(s, 2 H, OCH2Ph), 3.90 (ddd, J = 11.3, 8.9, 4.6 Hz, 1 H, 3-H), 4.86–
3.74 (m, 3 H, 5-H, 6-H), 3.55 (t, J = 8.9 Hz, 1 H, 4-H), 2.16 (ddd,
J = 13.2, 4.6, 1.5 Hz, 1 H, 2-Ha), 1.78 (br. s, 1 H, OH), 1.70 (ddd,
J = 13.2, 11.3, 4.2 Hz, 1 H, 2-Hb) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 138.4, 138.3, 128.61 (2), 128.58 (2), 128.2 (2), 128.0,
127.9, 127.8 (2), 87.4, 77.5, 76.8, 75.1, 73.8, 72.1, 62.0, 34.9 ppm.
IR (neat): ν = 3460 (broad, O–H), 2107 (N ) cm–1. HRMS (ESI):
˜
3
m/z calcd. for C20H23O4N3 [M + Na]+ 392.158; found 392.159.
Compound 21β: Rf = 0.47 (toluene/acetone, 9:1). [α]2D0 = –27.9 (c =
1
1, CHCl3). H NMR (300 MHz, CDCl3): δ = 7.39–7.24 (m, 10 H, H), 3.98 (t, J = 9.3 Hz, 1 H, 3Ј-H), 3.86 (ddd, J = 12.6, 6.3, 3.2 Hz,
ArH), 4.95 (d, J = 10.9 Hz, 1 H, OCH2Ph), 4.74–4.60 (m, 4 H, 1 H, 6-Ha), 3.82–3.66 (m, 5 H, 4-H, 5-H, 5Ј-H, 6Ј-H), 3.66 (ddd,
OCH2Ph, 1-H), 3.90 (br. d, J = 11.8 Hz, 1 H, 6-Ha), 3.78 (m, 1 H, J = 12.6, 7.7, 2.3 Hz, 1 H, 6-Hb), 3.59 (t, J = 9.3 Hz, 1 H, 4Ј-H),
6-Hb), 3.69 (ddd, J = 11.4, 8.7, 4.9 Hz, 1 H, 3-H), 3.53 (dd, J =
9.5, 8.7 Hz, 1 H, 4-H), 3.40 (ddd, J = 9.5, 4.3, 2.8 Hz, 1 H, 5-H),
2.31 (ddd, J = 12.8, 4.9, 2.1 Hz, 1 H, 2-Ha), 1.93 (br. t, J = 7.1 Hz,
1 H, OH), 1.60 (dt, J = 12.8, 11.2 Hz, 1 H, 2-Hb) ppm. 13C NMR
3.53 (dd, J = 9.3, 3.5 Hz, 1 H, 2Ј-H), 3.36 (s, 3 H, MeO), 2.08 (br.
dd, J = 7.8, 6.3 Hz, 1 H, OH), 0.20–0.17 (3ϫ s, 27 H, TMS) ppm.
13C NMR (100 MHz, CDCl3): δ = 144.2, 138.9, 138.3, 138.2,
128.53 (4), 128.45 (2), 128.2 (2), 128.1 (2), 128.0 (3), 127.8, 127.6,
(75.5 MHz, CDCl3): δ = 138.2, 138.1, 128.6 (4), 128.2 (2), 128.1, 124.9, 102.6, 101.8, 101.4, 98.3, 92.6, 91.7, 91.4, 84.0, 82.2, 82.0,
128.0, 127.8 (2), 86.6, 79.1, 77.7, 77.4, 75.3, 71.9, 62.2, 36.3 ppm. 79.9, 78.6, 77.6, 75.8, 75.2, 75.1, 74.4, 73.5, 70.1, 69.3, 65.0, 61.24,
1970
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