Benzaldehyde → HCID 67983087, compound

HRID 595371Notes

Reaction equation

HRID 595371 reaction equation
[CH3:1][N:2]([CH3:16])[C:3]1[S:4][C@H:5]2[O:11][C@H:10]([CH2:12][OH:13])[C@@H:9]([OH:14])[C@H:8]([OH:15])[C@H:6]2[N:7]=1.C(Cl)Cl.C([O-])(O)=O.[Na+].[CH:25](=O)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>[Cl-].[Cl-].[Zn+2]>[CH3:1][N:2]([CH3:16])[C:3]1[S:4][C@H:5]2[O:11][C@@H:10]3[CH2:12][O:13][CH:25]([C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)[O:14][C@H:9]3[C@H:8]([OH:15])[C@H:6]2[N:7]=1

Participants

6

Reactant 4

HCID 240BenzaldehydeHCID 6344DichloromethaneHCID 516892Sodium BicarbonateHCID 10848161HCID 10848161, compound

Product 1

HCID 67983087HCID 67983087, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 3007855ZincchlorideCatalyst

Procedure

A suspension of -(3aR,5R,6S,7R,7aR)-2-(dimethylamino)-5-(hydroxymethyl)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diol (0.800 g, 3.23 mmol) and anhydrous ZnCl2 (1.00 g, 7.35 mmol) in benzaldehyde (5 mL) was stirred at room temperature overnight. DCM (50 mL) and satd. aqueous NaHCO3 (50 mL) was added, and mixture was stirred for 20 min. The solid was filtered off, and the organic layer was collected from the filtrate. The aqueous layer was extracted with DCM (2×50 mL), and the combined extract was dried over anhydrous Na2SO4. After filtration the solvent was evaporated under reduced pressure, and the residue was purified on silica gel by flash column chromatography (1.0 M NH3 in MeOH/DCM, 3:100), affording -(3aR,4aR,8aS,9R,9aR)-2-(dimethylamino)-7-phenyl-3a,4a,5,8a,9,9a-hexahydro-[1,3]dioxino[4′,5′:5,6]pyrano[3,2-d]thiazol-9-ol as a pale yellow solid (0.76 g, 70%). 1H NMR (400 MHz, CDCl3) δ 7.51-7.48 (m, 2H), 7.40-7.34 (m, 3H), 6.39 (d, J=6.6 Hz, 1H), 5.58 (s, 1H), 4.31 (dd, J=5.1, 10.4 Hz, 1H), 4.10-4.03 (m, 2H), 3.86 (dd, J=8.2, 9.5 Hz, 1H), 3.76 (t, J=10.4 Hz, 1H), 3.59 (t, J=9.5 Hz, 1H), 3.00 (s, 6H).

Workup

  1. stirringmixture was stirred for 20 min
  2. filtrationThe solid was filtered off
  3. customthe organic layer was collected from the filtrate
  4. extractionThe aqueous layer was extracted with DCM (2×50 mL)
  5. extractionthe combined extract
  6. dry with materialwas dried over anhydrous Na2SO4
  7. filtrationAfter filtration the solvent
  8. customwas evaporated under reduced pressure
  9. customthe residue was purified on silica gel by flash column chromatography (1.0 M NH3 in MeOH/DCM, 3:100)

Sources & evidence

ORD record
ord-b7821a5c708d4391a7384a21ee267b05
Source dataset
uspto-grants-2016_01
Patent number
US09243020B2

Reaction notes

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