Benzoic anhydride → 10-benzoyl-10deacetylbaccatin III

HRID 363845

Reaction equation

HRID 363845 reaction equation
[CH3:1][C:2]1[C@@H:19]([OH:20])[CH2:18][C@:14]2([OH:21])[C:15]([CH3:17])([CH3:16])[C:3]=1[C@@H:4]([OH:39])[C:5]([C@@:7]1([CH3:38])[C@H:12]([C@@H:13]2[O:22][C:23]([C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)=[O:24])[C@:11]2([O:33][C:34]([CH3:36])=[O:35])[CH2:31][O:32][C@@H:10]2[CH2:9][C@@H:8]1[OH:37])=[O:6].[C:40](OC(=O)C1C=CC=CC=1)(=[O:47])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1.O.FC(F)(F)S([O-])(=O)=O.[Yb+3].FC(F)(F)S([O-])(=O)=O.FC(F)(F)S([O-])(=O)=O.C(Cl)Cl.CO>O1CCCC1>[CH3:1][C:2]1[C@@H:19]([OH:20])[CH2:18][C@:14]2([OH:21])[C:15]([CH3:16])([CH3:17])[C:3]=1[C@@H:4]([OH:39])[C:5]([C@@:7]1([CH3:38])[C@H:12]([C@@H:13]2[O:22][C:23]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:24])[C@:11]2([O:33][C:34]([CH3:36])=[O:35])[CH2:31][O:32][C@@H:10]2[CH2:9][C@@H:8]1[OH:37])=[O:6].[CH3:1][C:2]1[C@@H:19]([OH:20])[CH2:18][C@:14]2([OH:21])[C:15]([CH3:16])([CH3:17])[C:3]=1[C@@H:4]([O:39][C:40]([C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1)=[O:47])[C:5]([C@@:7]1([CH3:38])[C@H:12]([C@@H:13]2[O:22][C:23]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:24])[C@:11]2([O:33][C:34]([CH3:36])=[O:35])[CH2:31][O:32][C@@H:10]2[CH2:9][C@@H:8]1[OH:37])=[O:6]

Participants

7

Reactant 4

HCID 7167Benzoic anhydrideHCID 15427210-deacetylbaccatin IIIHCID 21226129Dichloromethane methanolHCID 45075687Ytterbium(3+) trifluoromethanesulfonate--water (1/3/1)

Product 2

HCID 15427210-deacetylbaccatin IIIYield 22%HCID 1554999310-benzoyl-10deacetylbaccatin IIIYield 62%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 50 mg (91.9 μmol) of 10-deacetylbaccatin III and 13 μL (1.5 eq.) of benzoic anhydride in 2.0 mL of freshly distilled tetrahydrofuran 100 μL of a solution of 5.8 mg of commercial ytterbium trifluoromethanesulfonate hydrate in 1.0 mL of tetrahydrofuran was added. The reaction mixture was stirred at room temperature for 48 hours. Usual workup and isolation of the product by means of preparative TLC (Silica 60, CH2Cl2/MeOH 10:1) afforded 11 mg unreacted 10-deacetylbaccatin III (22%) along with 29 mg of 10-benzoyl-10deacetylbaccatin III (62%), m.p. 154°-156° C. C36H40O11 calculated C 66.66% H 6.22% measured C 66.50% H 6.23%. 1H-NMR (300 MHz, CDCl3) δ (ppm)=1.18 (s, 3H), 1.25 (s, 3H), 1.69 (s, 3H), 1.80-1.93 (m, 1H), 2.09 (s, 3H), 2.16-2.23 (m, 2H), 2.29 (s, 3H), 2.53-2.61 (m, 1H), 3.95 (d, 1H, J=6.9), 4.17 (d, 1H, J=8.3), 4.32 (d, 1H, J=8.3), 4.55 (dd, 1H, J=6.6, 10.6), 4.91 (br t, 1H, J=7.9), 5.00 (d, 1H, J=9.2), 5.67 (d, 1H, J=6.9), 6.59 (s, 1H), 7.40-7.52 (m, 4H), 7.54-7.61 (m, 2H), 8.04-8.14 (m, 4H).

Sources & evidence

ORD record
ord-1a9cc81b4efa48e3adb222b2b96ff47b
Source dataset
uspto-grants-1999_02
Patent number
US05874595

Linked notes

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