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

HRID 1713613Notes

Reaction equation

HRID 1713613 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@H:40]2[O:58][CH3:59])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@H:40]([O:58][CH3:59])[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 68794572(2R,2'S,3'R,4'S,5'R,6'R)-3',4',5'-tris(benzyloxy)-6'-(benzyloxymethyl)-6-chloro-5-(4-ethylbenzyl)-2-methoxy-3',4',5',6'-tetrahydro-2H-spiro[benzofuran-3,2'-pyran]HCID 178418361HCID 178418361, compound

Product 1

HCID 68792003(2R,2'S,3'R,4'S,5'S,6'R)-6-chloro-5-(4-ethylbenzyl)-6'-(hydroxymethyl)-2-methoxy-3',4',5',6'-tetrahydro-2H-spiro[benzofuran-3,2'-pyran]-3',4',5'-triolYield 76.4%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 54 (22 mg, 27 μmol) in a mixture of MeOH (1.5 mL) and THF (0.5 mL) were added Pd(OH)2/C (15 mg) and 1,2-dichlorobenzene (20 μL). A balloon of hydrogen gas was attached for 0.5 h with vigorous stirring. LC/MS indicated that de-protection was complete. The reaction mixture was filtered through Celite, concentrated to a residue, and purified by preparatory TLC (5% MeOH in DCM) to give 55 (9.3 mg, 76%). 1H NMR (300 MHz, CD3OD) δ 7.20 (s, 1H), 7.06 (s, 4H), 6.82 (s, 1H), 5.61 (s, 1H), 3.99 (s, 2H), 3.63-3.79 (m, 3H), 3.55 (s, 3H), 3.42-3.60 (m, 3H), 2.57 (q, J=7.5 Hz, 2H), 1.19 (t, J=7.5 Hz, 3H). LCMS m/z 451 (M+H), 473 (M+Na).

Workup

  1. filtrationThe reaction mixture was filtered through Celite
  2. concentrationconcentrated to a residue
  3. custompurified by preparatory TLC (5% MeOH in DCM)

Sources & evidence

ORD record
ord-42eddd1796b94238932e01f8ca33ad2d
Source dataset
uspto-grants-2010_09
Patent number
US07795228B2

Reaction notes

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