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

HRID 1713602Notes

Reaction equation

HRID 1713602 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][CH:41]([CH2:59][OH:60])[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][CH:41]([CH2:59][OH:60])[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

7

Reactant 3

HCID 72391,2-DichlorobenzeneHCID 68793779((2'S,3'R,4'S,5'R,6'R)-3',4',5'-tris(benzyloxy)-6'-(benzyloxymethyl)-7-chloro-6-(4-ethylbenzyl)-3',4',5',6'-tetrahydrospiro[chroman-4,2'-pyran]-2-yl)methanolHCID 178418361HCID 178418361, compound

Product 1

HCID 68794586(2'S,3'R,4'S,5'S,6'R)-7-chloro-6-(4-ethylbenzyl)-2,6'-bis(hydroxymethyl)-3',4',5',6'-tetrahydrospiro[chroman-4,2'-pyran]-3',4',5'-triolYield 64%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 39 (17 mg, 21 umol) 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 (30 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 40 (6.2 mg, 64%).1H NMR (300 MHz, CD3OD) δ 7.37 (s, 1H), 7.06 (s, 4H), 6.88 (s, 1H), 4.16-4.34 (m, 1H), 3.98 (AB pattern, J=12.0 Hz, 2H), 3.88 (d, (d, J=9.6 Hz, 1H), 3.74-3.80 (m, 3H), 3.51-3.61 (m, 3H), 3.30-3.35 (m, 1H, under the solvent), 2.57 (q, J=7.5 Hz, 2H), 2.28 (d, J=13.5 Hz, 1H), 2.11 (dd, J=12.3, 15.0 Hz, 1H), 1.19 (t, J=7.5 Hz, 3H). LC/MS m/z 465 (M+H), 487 (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-ce7c01b08e8d41988549f4a729866e0d
Source dataset
uspto-grants-2010_09
Patent number
US07795228B2

Reaction notes

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