Phenolate → 7-beta-Galactopyranosyloxycoumarin-4-acetic acid

HRID 610659Notes

Reaction equation

HRID 610659 reaction equation
[OH:1][C:2]1[CH:11]=[C:10]2[C:5]([C:6]([CH2:13][C:14]([OH:16])=[O:15])=[CH:7][C:8](=[O:12])[O:9]2)=[CH:4][CH:3]=1.[C:17]([OH:20])(=O)[CH3:18].C(O)(=O)C.C(O)(=O)C.C(O)(=O)C.[OH:33][C@@H:34]1O[C@H](CO)[C@H:39]([OH:40])[C@H:37]([OH:38])[C@H:35]1[OH:36].C1([O-])C=CC=CC=1.C(O[C@@H]1[C@@H](OC(=O)C)[C@@H](OC(=O)C)[C@@H](COC(=O)C)O[C@@H]1Br)(=O)C.C(O[C@@H]1[C@@H](OC(=O)C)[C@@H](OC(=O)C)[C@@H](COC(=O)C)O[C@H]1OC1C=C2C(C(CC([O-])=O)=CC(=O)O2)=CC=1)(=O)C>>[C@@H:34]1([O:1][C:2]2[CH:11]=[C:10]3[C:5]([C:6]([CH2:13][C:14]([OH:16])=[O:15])=[CH:7][C:8](=[O:12])[O:9]3)=[CH:4][CH:3]=2)[O:33][C@H:18]([CH2:17][OH:20])[C@H:39]([OH:40])[C@H:37]([OH:38])[C@H:35]1[OH:36]

Participants

6

Reactant 5

HCID 119047PhenolateHCID 2734143alpha-AcetobromogalactoseHCID 5338490(7-Hydroxy-2-oxo-2H-1-benzopyran-4-yl)acetic acidHCID 70272550HCID 70272550, compoundHCID 86754922HCID 86754922, compound

Product 1

HCID 1968177-beta-Galactopyranosyloxycoumarin-4-acetic acid

Procedure

In accordance with exemplary Scheme 1, the carboxy function of 7-Hydroxycoumarin-4-acetic acid 1 (available from Aldrich Chemical Co., Milwaukee, Wis.) is protected by, for example, conversion to the methyl ester 2 via the Fischer Spier reaction using a procedure described by Baker, W., Haksar, C. N., McOmie, J. F. W., J. Chem. Soc. 170-173 (1950). An enzyme cleavable group can then be added to the remaining hydroxyl function at the 7 position. For example, β-D-galactopyranoside tetraacetate 3 is prepared by reaction of the phenolate anion of compound 2 with tetra-O-acetyl-α-D-galactopyranosyl bromide (available from Sigma Chemical Co., St. Louis, Mo.) using a procedure described by Baggett et al. in Carbohydrate Research 197, 295-301, (1990). The protected species then can be deprotected. As shown in Scheme 1, 7-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyloxy)coumarin-4-acetate 3 is hydrolysed to give 7-β-D-galactopyranosyloxycoumarin-4-acetic acid 4 using the procedure described by Baggett et al. in Carbohydrate Research 197, 295-301, (1990). Compound 4 can then be modified with a suitable amine functional group to yield the final product. Scheme 1 demonstrates conversion of compound 4 to the pentafluorophenyl ester and then reaction with ethanolamine to give the compound 5. Compound 5 can also be obtained from compound 3 as outlined in Scheme 1.

Workup

  1. customvia the Fischer Spier reaction

Sources & evidence

ORD record
ord-567b944ce2a2444d98bb2a25475487fc
Source dataset
uspto-grants-1999_12
Patent number
US05998593

Reaction notes

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