Formic Acid → (1S,2S,3S,4R,5S)-5-{4-Chloro-3-[4-(2-hydroxy-ethoxy)-benzyl]-phenyl}-1-hydroxymethyl-6,8-dioxa-bicyclo[3.2.1]octane-2,3,4-triol

HRID 59196Notes

Reaction equation

HRID 59196 reaction equation
C([O:8][CH2:9][CH2:10][O:11][C:12]1[CH:38]=[CH:37][C:15]([CH2:16][C:17]2[CH:18]=[C:19]([C@@:24]34[O:31][C@@:28]([CH2:32][OH:33])([CH2:29][O:30]3)[C@@H:27]([OH:34])[C@H:26]([OH:35])[C@H:25]4[OH:36])[CH:20]=[CH:21][C:22]=2[Cl:23])=[CH:14][CH:13]=1)C1C=CC=CC=1.C(O)=O>C(O)C.O1CCCC1.[Pd]>[Cl:23][C:22]1[CH:21]=[CH:20][C:19]([C@@:24]23[O:31][C@@:28]([CH2:32][OH:33])([CH2:29][O:30]2)[C@@H:27]([OH:34])[C@H:26]([OH:35])[C@H:25]3[OH:36])=[CH:18][C:17]=1[CH2:16][C:15]1[CH:37]=[CH:38][C:12]([O:11][CH2:10][CH2:9][OH:8])=[CH:13][CH:14]=1

Participants

6

Reactant 2

HCID 284Formic AcidHCID 67153902(1S,2S,3S,4R,5S)-5-(3-(4-(2-(Benzyloxy)ethoxy)benzyl)-4-chlorophenyl)-1-(hydroxymethyl)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol

Product 1

HCID 52931705(1S,2S,3S,4R,5S)-5-{4-Chloro-3-[4-(2-hydroxy-ethoxy)-benzyl]-phenyl}-1-hydroxymethyl-6,8-dioxa-bicyclo[3.2.1]octane-2,3,4-triolYield 82%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of intermediate (1S,2S,3S,4R,5S)-5-(3-(4-(2-(Benzyloxy)ethoxy)benzyl)-4-chlorophenyl)-1-(hydroxymethyl)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol (4 mg, 0.007 mmol) in a mixture of ethanol and tetrahydrofurane (1 mL, 4 to 1 in volume) was successively added formic acid (12 microL, 0.30 mmol) and palladium black (7.5 mg, 0.07 mmol). The reaction mixture was stirred at room temperature for 2 hours, the palladium was filtered through a pad of Celite®, the filtrate was evaporated and the residue was dried under high vacuum to afford 2.6 mg (80% yield) of the desired product. LCMS 453.5 (M+H+; positive mode). 1H NMR (500 MHz, METHANOL-d4) delta ppm 3.56 (d, J=7.8 Hz, 1 H), 3.58-3.72 (m, 4 H), 3.79 (d, J=7.8 Hz, 1 H), 3.82-3.88 (m, 2 H), 4.02 (t, J=4.9 Hz, 2 H), 4.05 (s, 2 H), 4.16 (d, J=7.6 Hz, 1 H), 6.84-6.89 (m, 2 H), 7.11 (d, J=8.5 Hz, 2 H), 7.35-7.42 (m, 2 H), 7.47 (d, J=2.0 Hz, 1 H).

Workup

  1. filtrationthe palladium was filtered through a pad of Celite®
  2. customthe filtrate was evaporated
  3. customthe residue was dried under high vacuum

Sources & evidence

ORD record
ord-5cbfeece4a154b24b7611c9eb1d16758
Source dataset
uspto-grants-2016_09
Patent number
US09439901B2

Reaction notes

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