1,2-Dichlorobenzene → (2'S,3'R,4'S,5'S,6'R)-6-chloro-5-(4-ethylbenzyl)-3',4',5'-trihydroxy-6'-(hydroxymethyl)-3',4',5',6'-tetrahydro-2H-spiro[benzofuran-3,2'-pyran]-2-one

HRID 1713607Notes

Reaction equation

HRID 1713607 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:43]1[CH:44]=[C:45]([CH2:49][C:50]3[CH:55]=[CH:54][C:53]([CH2:56][CH3:57])=[CH:52][CH:51]=3)[C:46]([Cl:48])=[CH:47][C:42]=1[O:41][C:40]2=[O:58])C1C=CC=CC=1.ClC1C=CC=CC=1Cl.[H][H]>CO.C1COCC1.[OH-].[OH-].[Pd+2]>[Cl:48][C:46]1[C:45]([CH2:49][C:50]2[CH:51]=[CH:52][C:53]([CH2:56][CH3:57])=[CH:54][CH:55]=2)=[CH:44][C:43]2[C@@:10]3([C:40](=[O:58])[O:41][C:42]=2[CH:47]=1)[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

Participants

7

Reactant 3

HCID 72391,2-DichlorobenzeneHCID 68792820(2'S,3'R,4'S,5'R,6'R)-3',4',5'-tris(benzyloxy)-6'-(benzyloxymethyl)-6-chloro-5-(4-ethylbenzyl)-3',4',5',6'-tetrahydro-2H-spiro[benzofuran-3,2'-pyran]-2-oneHCID 178418361HCID 178418361, compound

Product 1

HCID 68791193(2'S,3'R,4'S,5'S,6'R)-6-chloro-5-(4-ethylbenzyl)-3',4',5'-trihydroxy-6'-(hydroxymethyl)-3',4',5',6'-tetrahydro-2H-spiro[benzofuran-3,2'-pyran]-2-oneYield 80.3%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 48 (5 mg, 6.3 μmol) in a mixture of MeOH (1.5 mL) and THF (0.5 mL) were added Pd(OH)2/C (10 mg) and 1,2-dichlorobenzene (12 μL). A balloon of hydrogen gas was attached for 0.5 h with vigorous stirring. LCMS indicated that de-protection was complete. The reaction mixture was filtered through Celite, concentrated to a residue, and purified by passing through silica gel in a pipette (5% MeOH in DCM) to give 49 (2.2 mg, 80%). 1H NMR (300 MHz, CD3OD) δ 7.35 (s, 1H), 7.20 (s, 1H), 7.09 (s, 4H), 4.24-4.29 (m, 1H), 4.07 (t, J=10.5 Hz, 1H), 4.06 (s, 2H), 3.81 (dd, J=2.1, 12.0 Hz, 1H), 3.61-3.71 (m, 2H), 3.43 (t, J=9.9 Hz, 1H), 2.59 (q, J=7.5 Hz, 2H), 1.20 (t, J=7.5 Hz, 3H).

Workup

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

Sources & evidence

ORD record
ord-f0fe8fc1d83c4cecbbeeb5d8e9c53838
Source dataset
uspto-grants-2010_09
Patent number
US07795228B2

Reaction notes

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