D.M. Laventine et al. / Tetrahedron 65 (2009) 4766–4774
4773
2J6ax,6eq¼J5,6ax¼10.1, H-6ax), 3.78 (1H, d, J4,5¼9.4, H-4), 3.85 (1H, td,
(CH2, C-9), 43.7 (CH, C-2), 55.9 (CH3, C-7), 58.9 (CH, C-5), 68.7 (CH, C-
3), 69.8 (CH2, C6), 78.0 (CH, C4), 102.4 (CH, C7), 102.7 (CH, C1), 113.2
(2ꢂCH, o-Ph0), 118.1 (2ꢂCH, m-Ph0), 126.7 (2ꢂCH, o-Ph), 128.7
(2ꢂCH, m-Ph), 129.5 (CH, p-Ph0), 129.8 (CH, p-Ph), 137.7 (C, i-Ph),
148.2 (C, i-Ph0) ppm. MS (FABþ) m/z 368 [MH]þ. C22H26O4N [MH]þ
requires m/z 368.1862; HR-FABMS found m/z 368.1862.
2
J4,5¼J5,6ax¼9.8, J5,6eq¼4.9, H-5), 4.25 (1H, dd, J6ax,6eq¼10.1,
J5,6eq¼4.7, H-6eq), 40.65 (1H, s, H-1), 5.60 (1H, s, H-11), 06.72 (1H, t,
0
0
0
0
Jm-Ph ,p-Ph ¼7.3, p-Ph ), 6.84 (2H, d, Jm-Ph ,p-Ph ¼7.5, m-Ph ), 7.15 (2H,
m, o-Ph0), 7.30 (3H, m, m-Ph, p-Ph), 7.45 (2H, m, o-Ph) ppm. 13C
NMR (62.9 MHz, CDCl3) dC 19.9 (CH3, C-10), 34.1 (CH2, C-9), 40.8 (C,
C-3), 53.8 (CH2, C-8), 55.5 (CH3, C-7), 59.9 (CH, C-5), 67.4 (CH, C-2),
68.6 (CH2, C-6), 82.1 (CH, C-4), 98.9 (CH, C-1),102.4 (CH, C-11),126.7
(CH, o-Ph), 128.7 (CH, m-Ph), 129.2 (CH, p-Ph), 129.4 (CH, o-Ph0),
129.5 (CH, m-Ph0), 131.3 (CH, p-Ph0), 138.4 (C, Ph), 149.5 (C, Ph0). MS
(FABþ) m/z 323 [MH]þ. C23H28O4N2 [M]þ requires m/z 396.2049;
HR-FABMS found m/z 396.2049.
3.4.3.16. Methyl-a-D-3-amino-3-N-benzyl-(R)-4,6-O-benzylidene-2,3-
dideoxy-2-C,3-N-(ethane-1,2-diyl)-allopyranoside (15c). Compound
12 as starting material. Purification by flash column chromato-
graphy using 49:49:2 petrol–Et2O–Et3N. Yield 62%, colourless
syrup. Rf (49:49:2 petrol–Et2O–Et3N)¼0.25. 1H NMR (400 MHz,
CDCl3) dH 1.77 (2H, m, H-8
a
, H-8
b
), 2.34 (1H, td, 2J9 ¼J8 ¼8.9,
a
,9
b
b,9a
3.4.3.13. Methyl-
a-
D
-2-amino-(R)-4,6-O-benzylidene-2,3-dideoxy-2-
J8 ¼5.1, H-9
a
), 2.61 (1H, dtd, J2,8 ¼8.4, J1,2¼J2,3¼5.7, J2,8 ¼3.2, H-
a
,9
a
a
b
N,3-C-(ethane-1,2-diyl)-2-N-hydroxyl-(3R)-3-methyl-mannopyranoside
(11r). Compound 9 as starting material. Purification by flash col-
umn chromatography using 2:1 petrol–Et2O. Yield 93%, colourless
syrup. Rf (2:1 petrol–Et2O)¼0.21. 1H NMR (250 MHz, CDCl3) dH 1.28
(3H, s, H3-10), 1.60 (1H, ddd, 2J9 ¼13.5, J8 ¼11.3, J8 ¼3.8, H-
2), 3.24 (1H, q, 2J9 ¼J8 ¼J8 ¼8.0, H-9
b
), 3.30 (1H, t,
a
,9
b
a
,9
a
b,9a
2
J2,3¼J3,4¼4.2, H-3), 3.42 (4H, s and d, J10a,10b¼13.1, H3-7, H-10a),
2
3.76 (1H, t, J6ax,6eq¼J5,6ax¼10.5, H-6ax), 3.96 (1H, dd, J4,5¼9.5,
2
J3,4¼3.5, H-4), 4.38 (1H, dd, J6ax,6eq¼10.3, J5,6eq¼5.5, H-6eq), 4.53
2
(1H, td, J4,5¼J5,6ax¼9.9, J5,6eq¼5.4, H-5), 4.60 (1H, d, J10a,10b¼13.5,
a
a
,9
b
a
,9
b
b,9b
9
b
), 1.97 (1H, dt, 2J9 ¼13.2, J8(
¼8.5, H-9
a
), 2.62 (1H, s, H-2),
H-10b), 4.67 (1H, d, J1,2¼5.3, 1-H), 5.55 (1H, s, H-11), 7.30 (6H, m, m-
Ph, p-Ph, m-Ph0, p-Ph0), 7.43 (4H, m, o-Ph, o-Ph0) ppm. 13C NMR
(75.5 MHz, CDCl3) dC 24.7 (CH2, C-8), 43.9 (CH, C-2), 54.6 (CH2, C-9),
55.1 (CH3, C-7), 57.9 (CH, C-5), 60.7 (CH2, C-10), 60.9 (CH, C-3), 69.8
(CH2, C-6), 80.9 (CH, C-4), 99.6 (CH, C-1), 102.7 (CH, C-11), 126.3
(CH, o-Ph), 128.0 (2ꢂCH, o-Ph0), 128.3 (2ꢂCH, m-Ph), 128.8 (4ꢂCH,
m-Ph, p-Ph0), 129.0 (CH, p-Ph), 137.8 (2ꢂC, Ph, Ph0) ppm. MS (FABþ)
m/z 382 [MH]þ. C23H28O4N [MH]þ requires m/z 382.2018; HR-
FABMS found m/z 382.2018.
a
,9
b
,b
),9a
2.84 (1H, ddd, J8 ¼11.3, 2J8 ¼10.1, J8 ¼8.5, H-8
a
), 3.35 (3H, s,
a
,9
b
a
,8
b
a,9a
H3-7), 3.42 (1H, obs td, 2J8 ¼J8 ¼9.1, J8 ¼3.4, H-8
b), 3.50 (1H,
a
,8
b
b
,9
a
b,9b
d, J4,5¼9.8, H-4), 3.64 (1H, t, 2J6ax,6eq¼J5,6ax¼10.3, H-6ax), 3.87 (1H,
2
td, J4,5¼J5,6ax¼9.8, J5,6eq¼5.2, H-5), 4.21 (1H, dd, J6ax,6eq¼10.2,
J5,6eq¼5.2, H-6eq), 4.78 (1H, s, H-1), 5.42 (1H, s, H-11), 5.72 (1H, br s,
HO–N), 7.35 (3H, m, m-Ph, p-Ph), 7.50 (2H, m, o-Ph) ppm. 13C NMR
(62.9 MHz, CDCl3) dC 13.0 (CH3, C-10), 38.6 (CH2, C-9), 42.0 (C, C-3),
54.3 (CH3, C-7), 54.9 (CH2, C-8), 58.4 (CH, C-5), 68.5 (CH2, C-6), 74.5
(CH, C-2), 81.3 (CH, C-4), 100.4 (CH, C-1), 101.0 (CH, C-11), 125.2
(2ꢂCH, o-Ph), 127.2 (2ꢂCH, m-Ph), 128.0 (CH, p-Ph), 138.5 (C,
Ph) ppm. MS (FABþ) m/z 322 [MH]þ. C17H24O5N [MH]þ requires m/z
322.1654; HR-FABMS found m/z 322.1654.
3.4.3.17. Methyl-a-D-3-amino-(R)-4,6-O-benzylidene-2,3-dideoxy-2-C,3-
N-(ethane-1,2-diyl)-3-N-(phenethyl)-allopyranoside (15d). Compound
12 as starting material. Purification by flash column chromatography
using 49:49:2 petrol–Et2O–Et3N. Yield 62%, colourless syrup. Rf
(49:49:2 petrol–Et2O–Et3N)¼0.44. 1H NMR (250 MHz, CDCl3) dH 1.80
3.4.3.14. Methyl-a-D-3-amino-(R)-4,6-O-benzylidene-2,3-dideoxy-2-
C,3-N-(ethane-1,2-diyl)-3-N-ethyl-allopyranoside (15a). Compound
12 as starting material. Purification by flash column chromatogra-
phy using 74:24:2 petrol–Et2O–Et3N. Yield 37%, colourless syrup. Rf
(74:24:2 petrol–Et2O–Et3N)¼0.27. 1H NMR (400 MHz, CDCl3) dH
1.20 (3H, obs t, H3-11), 1.50 (1H, dt, 2J8 ¼14.6, J2,8 ¼J8 ¼7.4, H-
(1H, m, H-8
a
), 1.99 (1H, m, H-8
b
), 2.50 (1H, dtd, J2,8 ¼8.3,
a
J2,3¼J2,8 ¼6.6, J1,2¼0.9, H-2), 2.9 (6H, m, H-9
a
, H-9b, H2-10, H2-11),
b
3.30 (3H, s, H-7), 3.30 (1H, m, H-3), 3.63 (1H, t, 2J6ax,6eq¼J5,6ax¼9.1, H-
6ax), 3.71 (1H, m, H-4), 3.79 (1H,,td, J4,5¼J5,6ax¼9.1, J5,6eq¼4.3, H-5),
4.28 (1H, m, H-6eq), 4.49 (1H, s, H-1), 5.55 (1H, s, H-12), 7.02 (2H, m,
m-Ph0), 7.15 (3H, m, o-Ph0, p-Ph), 7.40 (3H, m, m-Ph, p-Ph), 7.55 (2H,
m, o-Ph) ppm. 13C NMR (62.9 MHz, CDCl3) dC 24.9 (CH2, C-8), 32.2
(CH2, C-11), 41.2 (CH, C-2), 49.3 (CH2, C-10), 52.7 (CH3, C-7), 54.3 (CH2,
C-9), 58.2 (CH, C-5), 59.0 (CH, C-3), 67.3 (CH2, C-6), 76.1 (CH, C-4), 98.5
(CH, C-1), 99.5 (CH, C-12), 123.7 (2ꢂCH, o-Ph0), 124.2 (CH, 2ꢂm-Ph0),
124.3 (CH, p-Ph0), 126.5 (2ꢂCH, o-Ph), 126.7 (2ꢂCH, m-Ph), 126.9 (CH,
p-Ph), 135.6 (C, i-Ph0), 138.4 (C, i-Ph) ppm. MS (FABþ) m/z 396 [MH]þ.
C24H30O4N [MH]þ requires m/z 396.2175; HR-FABMS found m/z
396.2175.
a,8
b
a
a,9a
8
a
), 1.62 (1H, dt 2J8 ¼14.7, J2,8 ¼J8 ¼7.4, H-8
b), 2.12 (1H, dt,
), 2.44 (3H, m, H-2, H2-10), 3.20
a
,8
b
b
b,9a
2J9 ¼10.8, J8 ¼J8 ¼7.4, H-9
a
a
,9
b
a
,9
a
b,9a
(1H, m, H-9
b
), 3.35 (3H, s, H3-7), 3.65 (1H, dd, J4,5¼9.4, J3,4¼2.8, H-
4), 3.73 (1H, t, 2J6ax,6eq¼J5,6ax¼9.9, H-6ax), 3.90 (1H, br s, H-3), 4.14
2
(1H, dt, J4,5¼J5,6ax¼9.9, J5,6eq¼5.1, H-5), 4.25 (1H, dd, J6ax,6eq¼9.6,
J5,6eq¼5.1, H-6eq), 4.60 (1H, s, H-1), 5.70 (1H, s, H-12), 7.35 (3H, m,
m-Ph, p-Ph), 7.50 (2H, m, o-Ph). 1H NMR (100 MHz, CDCl3) dC 11.6
(CH3, C-11), 27.6 (CH2, C-8), 43.8 (CH, C-2), 47.0 (CH2, C-10), 52.0
(CH2, C-9), 55.6 (CH3, C-7), 58.5 (CH, C-5), 69.4 (CH and CH2, C-3,
C-6), 76.6 (CH, C-4), 102.3 (CH, C-1), 102.4 (CH, C-12), 126.3 (2ꢂCH,
o-Ph), 128.3 (2ꢂCH, m-Ph), 129.1 (CH, p-Ph), 135.2 (C, i-Ph). MS
(FABþ) m/z 320 [MH]þ. C18H26O4N [MH]þ requires m/z 320.1862;
HR-FABMS found m/z 320.1862.
3.4.3.18. Methyl-a-D-3-amino-(R)-4,6-O-benzylidene-2,3-dideoxy-C,3-
N-(ethane-1,2-diyl)-3-N-(phenylamino)-allopyranoside (15e). Compound
12 as starting material. Purification by flash column chromatography
using 74:24:2 petrol–Et2O–Et3N. Yield 72%, colourless syrup. Rf (74:24:2
petrol–Et2O–Et3N)¼0.48. 1H NMR (400 MHz, CDCl3) dH 1.70 (2H, m,
3.4.3.15. Methyl-a-D-3-amino-(R)-4,6-O-benzylidene-2,3-dideoxy-2-
C,3-N-(ethane-1,2-diyl)-3-N-phenyl-allopyranoside (15b). Compound
12 as starting material. Purification by flash column chromatography
using 49:49:2 petrol–Et2O–Et3N. Yield 36%, colourless syrup. Rf
(49:49:2 petrol–Et2O–Et3N)¼1.7. 1H NMR (250 MHz, CDCl3) dH 1.75
H2-8
a
,
b
), 2.51 (1H, m, H-2), 2.68 (1H, dd, 2J9 ¼10.1, J8 ¼5.8, H-9
a),
a
,9
b
a,9a
2.87 (1H, td, 2J9 ¼J8 b 9.8, J8 ¼5.6, H-9
), 3.32 (1H, t, J2,3¼J4,5 H-3),
b
a
,9
b
a,9
b,9b
3.35 (3H, s, H3-7), 3.65 (2H, m, H-4, H-6ax), 3.90 (1H, m, H-5), 4.30 (1H,
dd, 2J6ax,6eq¼10.0, J5,6eq¼4.8, 6eq-H), 4.48 (1H, s, H-1), 5.60 (1H, s, H-10),
7.28 (2H, m, o-Ph0), 7.30 (3H, m, m-Ph0, p-Ph0), 7.35 (3H, m, m-Ph, p-Ph),
7.50 (2H, m, o-Ph) ppm. 13C NMR (100 MHz, CDCl3) dC 26.4 (CH2, C-8),
43.1 (CH, C-2), 54.8 (CH3, C-7), 58.9 (CH2, C-9), 61.3 (CH, C-5), 61.9 (CH, C-
3), 69.5 (CH2, C-6), 78.8 (CH, C-4), 101.3 (CH, C-1), 102.7 (CH, C-10), 125.0
(2ꢂCH, o-Ph0), 126.1 (2ꢂCH, m-Ph0), 126.3 (CH, p-Ph0), 126.8 (2ꢂCH,
o-Ph), 128.2 (2ꢂCH, m-Ph), 128.8 (CH, p-Ph), 135.2 (C, Ph0), 137.8 (C,
Ph) ppm. MS (FABþ) m/z 383 [MH]þ. C22H27O4N2 [M]þ requires m/z
383.1971; HR-FABMS found m/z 383.1970.
(2H, m, H2-8
3.20 (2H, t, J2,3¼J3,4¼7.1, H2-9
a
,
b
), 2.28 (1H, ddd, J2,8 ¼8.3, J2,3¼6.2, J2,8 ¼2.5, H-2),
a
b
a,b), 3.40 (3H, s, H3-7), 3.68 (1H, dd,
2
J4,5¼9.6, J3,4¼2.8, H-4), 3.78 (1H, t, J6ax,6eq¼J5,6eq¼9.9, H-6ax), 4.02
(1H, m, H-3), 4.22 (1H, td, J4,5¼J5,6ax¼9.9, J5,6eq¼5.1, H-5), 4.32 (1H,
dd, J 5.1, 9.9, H-6eq), 4.60 (1H, s, H-1), 5.61 (1H, s, H-10), 6.65 (2H,0t,
0
0
0
0
0
0
0
Jo-Ph ,m-Ph ¼Jm-Ph ,p-Ph ¼7.3, m-Ph ), 6.78 (1H, t, Jm-Ph ,p-Ph ¼7.8, p-Ph ),
0
0
0
7.10 (2H, d, Jo-Ph ,m-Ph ¼7.3, o-Ph ), 7.40 (3H, m, m-Ph, p-Ph), 7.55 (2H,
m, o-Ph) ppm. 1H NMR (62.9 MHz, CDCl3) dC 30.1 (CH2, C-8), 42.6