N. Petry et al. / Carbohydrate Research 445 (2017) 61e64
63
20
glycosyl derivatives from D-glucose and bearing a functionalized
arm at the anomeric position. According to the original work of
Kishi et al. and Gervay-Hague et al., the C-allylation reaction pro-
ceeded with the anticipated anomeric selectivities. Nevertheless,
when we next turned to the functionalization of alkenes, we picked
out mistakes in the literature concerning stereochemistry assign-
ment of C-glucopyranosides and derivatives. In this note, we thus
[a
]
¼ þ30.2 (c 0.98, CHCl3). IR: film (
n
, cmꢁ1): 3028, 2902, 2862,
D
1452, 1354, 1061. 1H NMR (400 MHz, CDCl3)
d 1.85e1.95 (m, 3H, H-3
and H-2a), 2,02 (m, 1H, H-2b), 3.45e3.55 (m, 2H, H-1), 3.57e3.66
(m, 2H, H-8 and H-7), 3.67 (dd, 1H, J9a,8 ¼ 2.0 Hz, J9a,9b ¼ 10.5 Hz, H-
9a), 3.72 (dd, 1H, J9b,8 ¼ 3.5 Hz, H-9b), 3.77 (dd, 1H, J5,4 ¼ 5.5 Hz,
J5,6 ¼ 9.5 Hz, H-5), 3.81 (m, 1H, H-6), 4.05 (m, 1H, H-4), 4.50 (d, 1H,
JCH2 ¼ 11.0 Hz, CH2Ph), 4.51 (d, 1H, JCH2 ¼ 12.0 Hz, CH2Ph), 4.65 (d,
2H, JCH2 ¼ 12.0 Hz, CH2Ph), 4.74 (d, 1H, JCH2 ¼ 11.5 Hz, CH2Ph), 4.83
(d, 1H, JCH2 ¼ 11.0 Hz, CH2Ph), 4.85 (d, 1H, JCH2 ¼ 11.0 Hz, CH2Ph),
4.95 (d, 1H, JCH2 ¼ 11.0 Hz, CH2Ph), 7.14e7.17 (m, 2H, HAr), 7.28e7.39
would like to give the correct characterizations of
alcohol and azide glucopyranosides 4 and 6 and to describe the
synthesis and the full characterization of new - and -C-propyl
bromide derivatives 5 and 5
b-C-propyl
b
b
a
b
a
b.
(m, 18H, HAr). 13C NMR (100.6 MHz, CDCl3)
d 23.1 (C-3), 28.8 (C-2),
33.8 (C-1), 69.0 (C-9), 71.2 (C-8), 73.3 (CH2Ph), 73.5 (CH2Ph), 73.5
(C-4), 75.1 (CH2Ph), 75.5 (CH2Ph), 78.1 (C-7), 80.1 (C-5), 82.5 (C-6),
127.6 (CAr), 127.7 (CAr), 127.8 (CAr), 127.9 (CAr), 127.9 (4 CAr), 128.0 (2
4. Experimental part
4.1. General methods
CAr), 128.0 (2 CAr), 128.4 (2 CAr), 128.4 (4 CAr), 128.5 (2 CAr), 138.0 (Cq-
Ar), 138.2 (Cq-Ar), 138.2 (Cq-Ar), 138.8 (Cq-Ar). Anal. Calcd for
All reactions were carried out in commercially available dry
solvents. TLC analyses were performed using standard procedures
on Kieselgel 60 F254 plates (Merck). Compounds were visualized
using UV light (254 nm) and (or) 30% methanolic H2SO4/heat as
developing agent. Column chromatography was performed on sil-
C37H41O5Br: C, 68.83; H, 6.40; Br, 12.38. Found: C, 69.20; H, 6.39; Br,
12.35. HRMS (ESI): calcd for C37H41O5BrK [MþNa]þ: 667.2035,
found: 667.2000.
4.4. 4,8-Anhydro-1-bromo-1,2,3-trideoxy-5,6,7,9-tetra-O-benzyl-
ica gel SI 60 (63e200
mm) (Merck) using hexanes (H), cyclohexane
D-glycero-D-gulo-nonitol (5b)
(cycloH) or ethyl acetate (EA) mixtures. FTIR spectra were recorded
on a Perkin-Elmer spectrum 1000 on NaCl windows. Melting points
were determined with a Tottoli apparatus and are uncorrected.
Optical rotations were measured on an Anton Paar MC300 polar-
imeter. 1H and 13C NMR spectra were recorded on a Bruker spec-
trometer DPX250 (250 MHz and 62.9 MHz, respectively) and
Avance III400 (400 MHz and 100.6 MHz, respectively). For complete
assignment of 1H and 13C signals, two-dimensional 1H,1H COSY and
mp ¼ 94e96 ꢀC (EtOH). Rf ¼ 0.35 (EtOAc/cyclohexane, 9/1).
20
[
a
]
¼ ꢁ3.6 (c 0.90, CHCl3). IR: film (
n
, cmꢁ1): 2909, 2868, 1495,
D
1450, 1433, 1358. 1H NMR (400 MHz, CDCl3)
d 1.58 (m, 1H, H-3a),
1.90e2.15 (m, 3H, H-3b and H-2), 3.27 (m, 1H, H-4), 3.30 (app t, 1H,
J5,4 ¼ J5,6 ¼ 9.5 Hz, H-5), 3.41 (ddd, 1H, J8,7 ¼ 9.5 Hz, J8,9a ¼ 4.0 Hz,
J8,9b ¼ 2.0 Hz, H-8), 3.45 (t, 2H, J1,2 ¼ 7.0 Hz, H-1), 3.63 (app t, 1H,
J7,6 ¼ J7,8 ¼ 9.5 Hz, H-7), 3.69 (dd, 1H, J9a,9b ¼ 11.0 Hz, H-9a), 3.71
(app t, 1H, H-6), 3.71 (dd, 1H, H-9b), 4.57 (d, 1H, JCH2 ¼ 12.0 Hz,
CH2Ph), 4.59 (d, 1H, JCH2 ¼ 12.0 Hz), 4.64 (d, 1H, JCH2 ¼ 12.0 Hz,
CH2Ph), 4.68 (d, 1H, JCH2 ¼ 11.0 Hz, CH2Ph), 4.85 (d, 1H,
JCH2 ¼ 12.0 Hz, CH2Ph), 4.90e4.93 (m, 3H, CH2Ph), 7.19e7.21 (m, 2H,
1H,13C correlation spectra were recorded. Chemical shifts (
d) are
given in ppm relative to the solvent residual peak. For clarity, atom
numbering is that given on Fig. 1 rather than resulting from the
IUPAC naming of compounds given in SI. The following abbrevia-
tions are used for multiplicity of NMR signals: s ¼ singlet,
d ¼ doublet, t ¼ triplet, q ¼ quadruplet, m ¼ multiplet, br ¼ broad
signal and app ¼ apparent multiplicity. MS spectra were recorded
on a Waters Platform and HRMS on a Bruker MicroTOFQ apparatus.
H
Ar), 7.28e7.38 (m,18H, HAr). 13C NMR (100.6 MHz, CDCl3)
d 29.3 (C-
3), 30.5 (C-2), 34.2 (C-1), 69.2 (C-9), 73.6 (CH2Ph), 75.1 (CH2Ph),
75.5 (CH2Ph), 75.7 (CH2Ph), 78.7 (C-7), 78.8 (C-4), 79.0 (C-8), 82.1
(C-5), 87.4 (C-6), 127.8 (CAr), 127.8 (CAr), 127.9 (2 CAr), 127.9 (3 CAr),
128.1 (3 CAr), 128.3 (2 CAr), 128.5 (2 CAr), 128.6 (2 CAr), 128.6 (2 CAr),
128.6 (2 CAr), 138.1 (Cq-Ar), 138.3 (Cq-Ar), 138.3 (Cq-Ar), 138.7 (Cq-Ar).
Anal. Calcd for C37H41O5Br: C, 68.83; H, 6.40; Br, 12.38. Found: C,
68.73; H, 6.55; Br, 12.42. HRMS (ESI): calcd for C37H41O5BrK
[MþK]þ: 683.1774, found: 683.1778.
4.2. 4,8-Anhydro-2,3-dideoxy-5,6,7,9-tetra-O-benzyl-D-glycero-D-
gulo-nonitol (4b)
mp ¼ 81e83 ꢀC (EtOH/H2O). Rf ¼ 0.28 (EtOAc/cyclohexane, 3/7).
20
[
a]
¼ þ3.4 (c 1.04, CHCl3). IR: film (
n
, cmꢁ1): 3393, 3028, 2903,
D
2857, 1497, 1452, 1356, 1092, 1057. 1H NMR (400 MHz, CDCl3)
d
1.56
4.5. 4,8-Anhydro-1-azido-1,2,3-trideoxy-5,6,7,9-tetra-O-benzyl-D-
(m, 1H, H-3a), 1.74 (m, 2H, H-2), 1.93e2.05 (m, 2H, H-3b and HOH),
3.31e3.34 (m, 2H, H-4 and H-5), 3.47 (ddd, 1H, J8,7 ¼ 9.5 Hz,
J8,9a ¼ 5.0 Hz, J8,9b ¼ 2.0 Hz, H-8), 3.61 (app t,1H, J7,8 ¼ J7,6 ¼ 9.5 Hz, H-
7), 3.63e3.74 (m, 5H, H-1, H-6 and H-9), 4.56 (d, 1H, JCH2 ¼ 12.0 Hz,
CH2Ph), 4.57 (d,1H, JCH2 ¼11.0 Hz, CH2Ph), 4.62 (d,1H, JCH2 ¼12.0 Hz,
CH2Ph), 4.68 (d,1H, JCH2 ¼11.0 Hz, CH2Ph), 4.84 (d,1H, JCH2 ¼11.0 Hz,
CH2Ph), 4.90e4.94 (m, 3H, CH2Ph), 7.17e7.19 (m, 2H, HAr), 7.28e7.37
glycero-D-gulo-nonitol (6b)
mp ¼ 44e46ꢀC (EtOH). Rf ¼ 0.38 (EtOAc/cyclohexane, 1/9).
20
[a
]
¼ ꢁ4.9 (c 1.07, CHCl3). IR: film (
n
, cmꢁ1): 302, 8, 2909, 2855,
D
2083, 1494, 1452, 1358, 1086, 1047. 1H NMR (400 MHz, CDCl3)
d 1.52
(m, 1H, H-2a), 1.69 (m, 1H, H-3a), 1.83 (m, 1H, H-3b), 1.93 (m, 1H, H-
2b), 3.24e3.33 (m, 4H, H1, H-5 and H-4), 3.42 (ddd, 1H, J8,7 ¼ 9.5 Hz,
J8,9a ¼ 4.0 Hz, J8,9b ¼ 2.0 Hz, H-8), 3.64 (app t, 1H, J7,8 ¼ J7,6 ¼ 9.5 Hz,
H-7), 3.67e3.74 (m, 2H, H-9a and H-6), 3.74 (dd, 1H, J9b,9a ¼ 11.0 Hz,
H-9b), 4.57 (d,1H, JCH2 ¼ 12.0 Hz, CH2Ph), 4.60 (d,1H, JCH2 ¼ 12.0 Hz,
CH2Ph), 4.64 (d, 1H, JCH2 ¼ 12.0 Hz, CH2Ph), 4.67 (d, 1H,
JCH2 ¼ 11.0 Hz, CH2Ph), 4.85 (d,1H, JCH2 ¼ 11.0 Hz, CH2Ph), 4.90e4.96
(m, 18H, HAr). 13C NMR (100.6 MHz, CDCl3)
d 28.7 (C-3), 29.4 (C-2),
63.0 (C-1), 69.1 (C-9),73.6 (CH2Ph), 75.2 (CH2Ph), 75.5 (CH2Ph), 75.7
(CH2Ph), 78.7 (C-7),78.8 (C-8), 79.5 (C-5), 82.1 (C-4), 87.4 (C-6),127.8
(2 CAr), 127.9 (2 CAr), 127.9 (CAr), 128.0 (CAr), 128.0 (2 CAr), 128.1 (2
C
C
Ar), 128.1 (2 CAr), 128.5 (2 CAr), 128.6 (2 CAr), 128.6 (2 CAr), 128.6 (2
Ar),138.1 (Cq-Ar),138.2 (Cq-Ar),138.2 (Cq-Ar),138.7 (Cq-Ar). Anal. Calcd
(m, 3H, CH2Ph), 7.18e7.21 (m, 2H, HAr), 7.28-7.37 (m, 18H, HAr). 13
C
for C37H42O6: C, 76.26; H, 7.27. Found: C, 76.29; H, 7.35. HRMS (ESI):
NMR (100.6 MHz, CDCl3) d 25.2 (C-3), 28.7 (C-2), 51.5 (C-1), 69.0 (C-
calcd for C37H42O6Na [MþNa]þ: 605.2879, found: 605.2871.
9), 73.5 (CH2Ph), 75.0 (CH2Ph), 75.3 (CH2Ph), 75.6 (CH2Ph), 78.6 (C-
7), 78.8 (C-4), 78.9 (C-8), 82.0 (C-5), 87.3 (C-6), 127.6 (CAr), 127.6
(CAr), 127.7 (2 CAr), 127.7 (3 CAr), 127.9 (CAr), 127.9 (2 CAr), 128.1 (2
4.3. 2,6-Anhydro-9-bromo-7,8,9-trideoxy-1,3,4,5-tetra-O-benzyl-
D-glycero-L-gulo-nonitol (5
a
)
C
Ar), 128.4 (2 CAr), 128.4 (2 CAr), 128.4 (2 CAr), 128.5 (2 CAr), 138.0 (Cq-
Ar), 138.1 (Cq-Ar), 138.2 (Cq-Ar), 138.6 (Cq-Ar). Anal. Calcd for
37H41N3O5: C, 73.12; H, 6.80; N, 6.91. Found: C, 73.41; H, 6.75; N,
mp ¼ 65e67 ꢀC (EtOH). Rf ¼ 0.40 (EtOAc/cyclohexane, 1/9).
C