(2'S,3'R,4'S,5'R,6'R)-3',4',5'-tris(benzyloxy)-6'-(benzyloxymethyl)-7-chloro-6-(4-ethylbenzyl)-2-methyl-3',4',5',6'-tetrahydrospiro[chroman-4,2'-pyran]-2-ol → (2'S,3'R,4'S,5'S,6'R)-7-chloro-6-(4-ethylbenzyl)-6'-(hydroxymethyl)-2-methyl-3',4',5',6'-tetrahydrospiro[chroman-4,2'-pyran]-2,3',4',5'-tetraol

HRID 1713611Notes

Reaction equation

HRID 1713611 reaction equation
C([O:8][C@@H:9]1[C@@H:14]([O:15]CC2C=CC=CC=2)[C@H:13]([O:23]CC2C=CC=CC=2)[C@@H:12]([CH2:31][O:32]CC2C=CC=CC=2)[O:11][C@:10]21[C:48]1[C:43](=[CH:44][C:45]([Cl:58])=[C:46]([CH2:49][C:50]3[CH:55]=[CH:54][C:53]([CH2:56][CH3:57])=[CH:52][CH:51]=3)[CH:47]=1)[O:42][C:41]([CH3:60])([OH:59])[CH2:40]2)C1C=CC=CC=1.[H][H]>CO.C1COCC1.[OH-].[OH-].[Pd+2]>[Cl:58][C:45]1[CH:44]=[C:43]2[O:42][C:41]([CH3:60])([OH:59])[CH2:40][C@@:10]3([C@H:9]([OH:8])[C@@H:14]([OH:15])[C@H:13]([OH:23])[C@@H:12]([CH2:31][OH:32])[O:11]3)[C:48]2=[CH:47][C:46]=1[CH2:49][C:50]1[CH:51]=[CH:52][C:53]([CH2:56][CH3:57])=[CH:54][CH:55]=1

Participants

6

Reactant 2

HCID 68790023(2'S,3'R,4'S,5'R,6'R)-3',4',5'-tris(benzyloxy)-6'-(benzyloxymethyl)-7-chloro-6-(4-ethylbenzyl)-2-methyl-3',4',5',6'-tetrahydrospiro[chroman-4,2'-pyran]-2-olHCID 178418361HCID 178418361, compound

Product 1

HCID 68794931(2'S,3'R,4'S,5'S,6'R)-7-chloro-6-(4-ethylbenzyl)-6'-(hydroxymethyl)-2-methyl-3',4',5',6'-tetrahydrospiro[chroman-4,2'-pyran]-2,3',4',5'-tetraolYield 34.4%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 45 (30 mg, 36.3 μmol) in a mixture of MeOH (3.0 mL) and THF (1 mL) was added Pd(OH)2/C (30 mg). A balloon of hydrogen gas was attached for 0.5 h with vigorous stirring. LC/MS indicated that de-protection was complete. The aromatic chloride was partially cleaved. The reaction mixture was filtered through Celite, concentrated to a residue, and purified by preparatory HPLC to give 53 (5.8 mg, 34%). 1H NMR (300 MHz, CD3OD) δ 7.50 (s, 1H), 7.00-7.07 (m, 4H), 6.77 (s, 1H), 3.98 (s, 2H), 3.93 (dd, J=2.1, 11.7 Hz, 1H), 3.65-3.82 (m, 3H), 3.55 (dd, J=8.1, 9.6 Hz, 1H), 3.27 (t, J=9.6 Hz, 1H), 2.80 (d, J=11.1 Hz, 1H), 2.57 (q, J=7.5 Hz, 2H), 1.96 (d, J=11.4 Hz, 1H), 1.68 (s, 3H), 1.19 (t, J=7.5 Hz, 3H). LC/MS m/z 447 (M−OH).

Workup

  1. filtrationThe reaction mixture was filtered through Celite
  2. concentrationconcentrated to a residue
  3. custompurified by preparatory HPLC

Sources & evidence

ORD record
ord-af3605052d3144429bcd9ba79df9898f
Source dataset
uspto-grants-2010_09
Patent number
US07795228B2

Reaction notes

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