Synthesis of Glucose based Water Soluble Molecular Tweezers
321
(d,1H, J=2.2 Hz, H-3), 4.42 (d, 1H, J=3.6 Hz, H-2), 5.88 (d, 1H, J=3.6 Hz, H-1), 6.52-6.58
(AB q, 4H, J=8.2 Hz, 8.0 Hz, ArH), 6.89-6.96 (AB q, 4H, J=8.1 Hz, 8.0 Hz, ArH); 13C NMR
(CDCl3, 200 MHz) δ: 26.1 and 26.7 each (1C, q, CH3), 40.1 ( 1C, t, CH2(Ph)2), 47.6 (1C, t,
C-6), 68.5 (1C, d, C-5), 75.2 ( 1C, d, C-3), 80.7 (1C, d, C-4), 85.1 (1C, d, C-2), 104.8 (1C, d,
C-1), 111.7 (1C, s, OC(CH3)2O), 113.9 (2C, d , Ar Cb), 115.6 (2C,d, Ar Cb’), 129.6 (4C, d,
Ar Cc,c’), 131.6 (1C, s, Ar Cd’), 132.3 (1C, s, Ar Cd), 143.9 (1C, s, Ar Ca’), 145.9 (1C, s, Ar
Ca), Inept: 26.1, 26.7, 68.4, 75.1, 80.6, 85.0, 104.8, 113.9, 115.5, 129.6 (+ve), 40.1; 47.6 (-
ve); (M+) ion m/z 400 (M+) ; 198 (M+-203 (sugar).
The second fraction on elution with dichloromethane-ethyl acetate (50:50 v/v) gave the
27
substrate 2b as a syrup ( 933 mg, 31%); [α]D –17.4o (c 1.0, EtOH); UV (EtOH) λmax nm
1
(log ε) 250.0 (4.53), 213.0 (4.39); H NMR (CDCl3, 200MHz) δ:1.30 and 1.46 each (s, 6H,
CH3); 2.96 (br, 6H, OH and NH), 3.39-3.70 (br m, 6H, CH2(Ph)2 and H-6), 3.98 (dd, 2H, H-
5), 4.10 (br, 2H, H-4), 4.27 (d, 2H, J=2.1 Hz, H-3), 4.42 (d, 1H, J=3.6 Hz, H-2), 5.90 (d, 2H,
J 3.6 Hz, H-1), 6.57 and 6.94 each (d, 4H, J = 8.0, Ar H); 13C NMR (CDCl3, 200 MHz)
δ: 26.1 and 26.7 each (2C, q, CH3), 40.1 (1C, t, CH2(Ph)2 ), 47.7 (2C, t, C-6), 68.5 (2C, d, C-
5), 75.2 (2C, d, C-3), 80.8 (2C, d, C-4), 85.1 (2C,d, C-2), 104.8 (2C, d, C-1), 111.8 (2C, s,
OC(CH3)2O), 114.0 (4C, d , Ar Cb), 129.6 (4C, d, Ar Cc,), 132.0 (2C, s, Ar Cd), 145.9 (2C, s,
Ar Ca); Inept: 26.1, 26.7, 68.4, 75.1, 80.8, 85.1, 104.8, 114.0, 129.6 (+ve), 40.1, 47.8 (-ve);
(M+) ion m/z 602 (M+); 400 (M-sugar); 385 (400-CH3); 211 (H2C(C6H4)2(NH2)NH=CH2);
184 (211-NHCH2), 108 (184-Ph).
6-Deoxy-6-[N-methyl(4’-N’-methyl(p-toluidine)](1,2-O-isopropylidene-
furanose) (3a) and 6,6’-[N,N’-dimethyl-4”,4”’-methylenedianilino)bis-(1,2-O-
isopropylidene- -D-glucofuranose) (3b)
α-D-gluco-
α
Compound 3 (1.13 g, 5 mM) was heated to 100 oC and to it was added compound 1 (2.02 g,
o
10 mM). The temperature was raised to 120-125 C and the reaction mixture aged for 1 h
without solvent. TLC (ethyl acetate) indicated the formation of two products. Purification of
the residue by column chromatography with dichloromethane-ethyl acetate (50:50v/v) as
eluent afforded the substrate 3b (977 mg, 31%) as colored syrup. UV (EtOH) λmax nm (log ε)
1
307.4 (3.72), 263.8 (4.55), 213.2 (4.32); H NMR (CDCl3, 200 MHz) δ:1.26 and 1.44 each
(s, 6H, CH3), 2.87 (s, 6H, NCH3), 3.29 - 3.51 (AB q, 4H, H-6); 3.73 (br s, 6H, CH2 and OH
), 3.95 (dd, 2H, J=2.4 Hz, H-5), 4.16 (br, 2H, H-4), 4.27 (s, 2H, H-3), 4.43 (d, 2H, J=3.4 Hz,
H-2); 5.88 (d, 2H, J=3.4 Hz, H-1), 6.69 and 7.01each (AB q, 4H, J=8.2 Hz, ArH); 13C
NMR (CDCl3, 200 MHz) δ: 26.0 and 26.6 each (2C, q, CH3), 39.8 ( 1C, t, CH2(Ph)2), 40.0
(2C, q, NCH3), 57.2 (2C, t, C-6), 67.9 (2C, d, C-5), 75.0 (2C, d, C-3), 80.5 (2C, d, C-4), 84.9
(2C, d, C-2), 104.7 (2C, d, C-1), 111.5 and 111.8 each (2C, s, OC(CH3)2O), 113.6 and
113.9each (4C, d , Ar Cb,b’), 129.4 and 129.7 (4C, d, Ar Cc,c’), 131.1 and 131.4 each (2C, s, Ar
Cd,d’), 147.9 (2C, s, Ar Ca); Inept: 26.1; 26.7; 39.9 ; 67.9; 74.9; 80.6; 85.0; 104.8; 113.8; 129.4;
131.2; 147.9 (+ve); 40.0, 57.2 (-ve); (M+) ion m/z 631 (M+) ; 630; 442, 428 ( M+-sugar).
The second fraction on elution with ethyl acetate gave the substrate 3a as colored syrup
1
(578 mg, 27%); UV (EtOH) λmax nm (log ε) 302.6 (3.64); 259.8 (4.45); 213.2 (4.21); H
NMR (CDCl3, 200 MHz) δ:1.30 and 1.48 each (s, 3H, CH3), 2.78 (s, 3H, NHCH3), 2.88 (s,
3H, NCH3), 3.24 (br, 3H, OH and NH), 3.36-3.53 (AB q, 2H, H-6), 3.77 (s, 2H, CH2(Ph)2),
4.00 (dd, 1H, J=2.4 Hz, H-5), 4.22 (dd, 1H, H-4), 4.32 (d, 1H, H-3), 4.49 (d, 1H, J = 3.6 Hz,
H-2), 5.94 (d, 1H, J = 3.6 Hz, H-1), 6.52 (d, 2H, J = 8.4 Hz, ArH), 6.75 (d, 2H, J = 8.6 Hz,
ArH), 6.96-7.06 (dd, 4H, J = 8.6, 8.4 Hz, Ar H); 13C NMR (CDCl3, 200 MHz) δ: 26.2 and
26.8 each (1C, q, CH3), 31.0 (1C, q, NHCH3), 40.0 (2C, m,NCH3 and CH2(Ph)2 ), 57.3 (1C,
t, C-6), 68.5 (1C, d, C-5), 75.5 ( 1C, d, C-3), 80.5 (1C, d, C-4), 85.2 (1C,d, C-2), 104.9 (1C,