ACCEPTED MANUSCRIPT
apparent dq, J = 17.1, 1.5 Hz, 1H), 5.21 (s, 1H, H-1), 5.19 (apparent dq, J = 10.5, 1.7 Hz, 1H), 5.15
(
apparent t, J = 1.5 Hz, 1H), 4.87 (d, J = 10.8 Hz, 1H), 4.77 (d, J = 11.3 Hz, 1H), 4.71 (d, J = 11.3 Hz,
1
2
9
9
1
6
H), 4.63 (d, J = 12.2 Hz, 1H), 4.50 (d, J = 12.2 Hz, 1H), 4.49 (d, J = 10.8 Hz, 1H), 4.46 (dt J = 9.0,
.0 Hz, 1H), 4.18 (ddt, J = 12.9, 5.1, 1.5 Hz, 1H), 4.02 (ddt, J = 12.9, 6.1, 1.5 Hz, 1H), 3.97 (ddd, J =
.8, 3.9, 2.0 Hz, 1H), 3.76 (dd, J = 10.8, 3.9 Hz, 1H), 3.67 (dd, J = 10.8, 2.0 Hz, 1H), 3.62 (dd, J = 9.8,
1
3
.0 Hz, 1H); C NMR: (CDCl ) δ 142.4, 138.45, 138.44, 138.3, 134.0, 128.6, 128.49, 128.48, 128.1,
3
C
28.0, 127.9, 127.83, 127.80, 127.75, 117.6, 110.8, 100.7, 81.3, 80.1, 75.2, 73.63, 73.57, 70.9, 68.9,
−
1
7.8; IR (Film from CH Cl ): ν 3032, 2922, 2855, 1496, 1453, 1099, 1065, 1025, 735, 697 cm ;
2
+
2
max
+
HRMS: m/z C H O Na [M+Na] calcd 509.2304, found 509.2304.
3
1
34
5
General Procedure for Suzuki Reactions of 2-Bromomethylene Pyranosides: The chosen
palladium catalyst (ca. 15 mol%) was dissolved in 1,4-dioxane then successively treated with base
(
K CO , K PO ·H O or KF, 3.0 equiv.), an additive (if relevant) and the arylboronic acid or
2 3 3 4 2
aryltrifluoroboronate (2.0 equiv.). The solution was then treated with a pre-mixed solution of allyl
glycoside β-2c (1.0 equiv.) in 1,4-dioxane and heated to reflux. After 20–72 hours the solution was
cooled to room temperature, quenched with water (5 mL) and extracted with dichloromethane (3 x 10
mL). The organic fractions were combined, dried, filtered through Celite® and concentrated. The
crude mixture obtained in this way was purified by flash chromatography.
Allyl 3,4,6-tri-O-benzyl-(2E)-2-C-(phenylmethylidene)-2-deoxy-α-
D-arabino-hexopyranoside
(
17b) Following the general procedure for Suzuki reactions, with Pd(PPh ) (15 mol%), K CO (3.0
3
4
2
3
equiv.) and phenylboronic acid (2.0 equiv.), and flash chromatography (silica gel, 1:9 ethyl
acetate:hexanes), product 17b was prepared as a colourless oil (31%). R 0.35 (5:1 hexanes:ethyl
f
1
acetate); H NMR: (CDCl ) δ 7.42–7.18 (complex m, 20H), 6.83 (d, J = 1.7 Hz, 1H), 6.00 (dddd, J =
3
H
1
=
4
(
7.1, 10.5, 6.4, 5.1 Hz, 1H), 5.56 (s, 1H), 5.32 (apparent dq, J = 17.1, 1.5 Hz 1H), 5.21 (apparent dd, J
10.5, 1.5 Hz 1H), 4.93 (d, J = 10.7 Hz, 1H), 4.83 (d, J = 11.0 Hz, 1H), 4.79 (d, J = 11.0 Hz, 1H),
.613 (d, J = 12.2 Hz, 1H), 4.609 (m, 1H), 4.55 (d, J = 10.7 Hz, 1H), 4.49 (d, J = 12.2 Hz, 1H), 4.20
ddt, J = 12.6, 5.1, 1.3 Hz, 1H), 4.05 (ddt, J = 12.6, 6.4, 1.5 Hz, 1H), 4.01 (ddd, J = 9.5, 3.9, 2.0 Hz,
1
3
1
H), 3.77 (dd, J = 10.5, 3.9 Hz, 1H), 3.72 (m, 1H), 3.67 (dd, J = 10.5, 2.0 Hz, 1H); C NMR:
(
CDCl ) δ 138.5, 138.34, 138.25, 136.3, 135.0, 134.1, 129.0, 128.9, 128.6, 128.53, 128.47, 128.3),
3 C
1
6
6
28.08, 128.06, 128.0, 127.8, 127.7, 127.4, 124.7, 118.0, 96.2, 81.9, 80.2, 75.3, 74.3, 73.6, 71.5, 68.9,
7.8; IR (Film from CH Cl ): ν 3009, 2997, 2850, 2801, 1423, 1401, 1261, 1100, 1025, 1027, 802,
2
2
max
−
1
+
+
97 cm ; HRMS: m/z C H O Na [M+Na] calcd 585.2617, found 585.2623.
3
7
38
5
Allyl 3,4,6-tri-O-benzyl-(2E)-2-C-(4′-methoxyphenylmethylidene)-2-deoxy-α-
D-arabino-
hexopyranoside (17c) Following the general procedure for Suzuki reactions, with Pd dba (15
2
3
mol%), KF (3.0 equiv.) and para-methoxyphenylboronic acid (2.0 equiv.), and flash chromatography
silica gel, 1:14 ethyl acetate:hexanes), para-methoxyphenyl-coupled product 17c was prepared. R
(
0
f
1
.35 (9:1 hexanes:ethyl acetate); H NMR: (CDCl ) δ 7.37–7.27 (complex m, 8H), 7.22–7.15
3 H
(
complex m, 6H), 7.12–7.10 (complex m, 2H), 7.00–6.98 (complex m, 2H), 6.72 (m, 2H), 6.03 (dddd,
J = 17.3, 10.5, 6.1, 5.1 Hz, 1H), 5.51 (d, J = 1.7 Hz, 1H), 5.35 (apparent dq, J = 17.3, 1.7 Hz, 1H),
.20 (apparent dq, J = 10.5, 1.5 Hz, 1H), 4.65 (d, J = 12.2 Hz, 1H), 4.63 (br s, 1H), 4.55 (d, J = 12.2
Hz, 1H), 4.47 (d, J = 12.2 Hz, 1H), 4.42 (ddt, J = 13.0, 5.1, 1.5 Hz, 1H), 4.32 (d, J = 11.5 Hz, 1H),
.23 (d, J = 11.5 Hz, 1H), 4.19 (ddt, J = 13.0, 6.1, 1.5 Hz, 1H), 4.09 (d, J = 12.2 Hz, 1H), 3.86 (ddd, J
9.3, 5.4, 2.9 Hz, 1H), 3.81 (s, 3H), 3.74 (dd, J = 9.3, 1.2 Hz, 1H), 3.71 (partially overlapping dd, J =
5
4
=
1
3
1
1
1
1.0, 2.9 Hz, 1H), 3.67 (dd, J = 11.0, 5.4 Hz, 1H); C NMR: (CDCl ) δ 159.0, 138.6, 138.1, 137.9,
3 C
34.8, 133.2, 132.8, 130.4, 128.42, 128.41, 128.3, 128.2, 128.0, 127.87, 127.83, 127.60, 127.59,
17.1, 113.6, 98.0, 79.8, 73.2, 72.7, 71.4 (2 x C), 70.0, 69.9, 68.4, 55.4; IR (Film from CH Cl ): ν
max
2
2
1
6