Glucovanillin

Glucovanillin extracted from green pods and simultaneously transformed to vanillin by a combination of enzyme activities involving cell wall degradation and glucovanillin hydrolysis.

Solid

Vanilloside is a glycoside.

Vanillin 2, 3, 4, 6-tetra-O-acetyl-b-D-glucopyranoside 3 (1.36 g, 3.0 mmol) was dissolved in THF/CH3OH/H2O (33 mL, v:v:v 5:5:1), and then K2CO3 (0.83 g, 6.0 mmol)was added. After stirring at 40 Cfor 20 min, the reaction was quenched with 1M HCl and thenconcentrated. The residue was purified by silica gel column chromatography(CH2Cl2/CH3OH, 15:1) to afford 4 as a white solid(0.88 g, 94percent). [a]D20 -11.4 (c 1.0, H2O). 1H NMR (DMSO-d6, 400 MHz) d: 9.86 (s, 1H, CHO), 7.52 (dd, J 8.3, 1.5 Hz, 1H, Ph-H), 7.43 (d, J 1.4 Hz, 1H, Ph-H), 7.28 (d, J 8.4 Hz, 1H, Ph-H), 5.39 (d, J 4.4 Hz, 1H, -OH), 5.16 (d, J 3.7 Hz, 1H, -OH), 5.09 (d, J 5.2 Hz, 2H, -OH, H-1), 4.59 (t, J 5.6 Hz, 1H, -OH), 3.84 (s, 3H, -OMe), 3.66 (dd, J 11.2, 4.7 Hz, 1H, H-3), 3.48e3.45 (m, 1H, H-2), 3.40e3.37 (m, 1H, H-4), 3.30e3.25 (m, 2H, H-6), 3.20e3.14 (m, 1H, H-5); 13C NMR (DMSOd6, 150 MHz)) d: 191.66 (CHO), 151.78, 149.34, 130.56, 125.43, 114.58, 110.52, 99.41 (C-1), 77.17, 76.84, 73.11, 69.58, 60.62, 55.70; ESIHRMSm/z [MNa] calculated for C14H18NaO8 337.0894 found337.0901.General procedure: To a solution 2 and the acceptor ArOH (3.0 equiv) in dry DCM (0.1 M) was added afreshly prepared solution of BF3•OEt2 (1.0 equiv., 1M in dry DCM). The solution wasstirred 1 h and followed by TLC (30:70; EtOAc : hexanes). A solution of NaHCO3(aq) wasadded and the mixture was extracted with DCM, washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The α/β ratio was measured by 1H NMR on the crude.The residue was treated with a freshly prepared solution MeONa (0.25 equiv., 0.5 M inmethanol) in dry methanol (0.3 M). The solution was stirred at r.t. for 1 h andneutralized with Amberlite IR-120 H+, filtered and concentrated in vacuo to give a whitesolid. Quick flash column chromatography (10:90; MeOH:DCM) removed excess of ArOHand led to the β-D anomer, which was recrystallized in hot ethanol.

Vanillin 4-O-β-D-Glucoside is the glucosylated precursor of Vanillin (V097500) found in the seed pods of Vanilla planifola. During the curing process Vanillin 4-O-β-D-Glucoside is transformed into the aromatic vanillin.

Molecular Weight:314.29
XLogP3:-1.6
Hydrogen Bond Donor Count:4
Hydrogen Bond Acceptor Count:8
Rotatable Bond Count:5
Exact Mass:314.10016753
Monoisotopic Mass:314.10016753
Topological Polar Surface Area:126
Heavy Atom Count:22
Complexity:365
Undefined Atom Stereocenter Count:5
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes