1,2-Dichlorobenzene → (2'S,3'R,4'S,5'S,6'R)-7-chloro-6-(4-ethylbenzyl)-2,6'-bis(hydroxymethyl)-2-methyl-3',4',5',6'-tetrahydrospiro[chroman-4,2'-pyran]-3',4',5'-triol

HRID 1713610Notes

Reaction equation

HRID 1713610 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]([CH2:60][OH:61])([CH3:59])[CH2:40]2)C1C=CC=CC=1.ClC1C=CC=CC=1Cl.[H][H]>CO.C1COCC1.[OH-].[OH-].[Pd+2]>[Cl:58][C:45]1[CH:44]=[C:43]2[O:42][C:41]([CH2:60][OH:61])([CH3:59])[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:55]=[CH:54][C:53]([CH2:56][CH3:57])=[CH:52][CH:51]=1

Participants

7

Reactant 3

HCID 72391,2-DichlorobenzeneHCID 68794050((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-yl)methanolHCID 178418361HCID 178418361, compound

Product 1

HCID 25154357(2'S,3'R,4'S,5'S,6'R)-7-chloro-6-(4-ethylbenzyl)-2,6'-bis(hydroxymethyl)-2-methyl-3',4',5',6'-tetrahydrospiro[chroman-4,2'-pyran]-3',4',5'-triolYield 38%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 51 (13 mg, 15.5 μmol) in a mixture of MeOH (1.2 mL) and THF (0.4 mL) was 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 via preparatory TLC (5% MeOH in DCM) to give 52 (2.8 mg, 38%). 1H NMR (300 MHz, CD3OD) δ 7.34 (s, 1H), 7.07 (s, 4H), 6.81 (s, 1H), 3.97 (s, 2H), 3.85 (dd, J=2.1, 11.1 Hz, 1H), 3.67-3.74 (m, 3H), 3.44-3.56 (m, 3H), 3.23 (t, J=9.3 Hz, 1H), 2.58 (q, J=7.5 Hz, 2H), 2.45 (d, J=15.3 Hz, 1H), 2.16 (d, J=15.6 Hz, 1H), 1.42 (s, 3H), 1.19 (t, J=7.5 Hz, 3H). LCMS m/z 479 (M+H), 501 (M+Na).

Workup

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

Sources & evidence

ORD record
ord-fd1bf9468058439e818d02dbdcb50603
Source dataset
uspto-grants-2010_09
Patent number
US07795228B2

Reaction notes

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