Tin tetrachloride → HCID 178482335, compound

HRID 2194651Notes

Reaction equation

HRID 2194651 reaction equation
C(O[C@H:5]1[C@H:10]([NH:11][C:12]([NH:14][CH3:15])=[S:13])[C@@H:9]([O:16][C:17](=[O:19])[CH3:18])[C@H:8]([O:20][C:21](=[O:23])[CH3:22])[C@@H:7]([CH2:24][O:25][C:26](=[O:28])[CH3:27])[O:6]1)(=O)C.Cl[Sn](Cl)(Cl)Cl>C(Cl)Cl>[C:21]([O:20][C@@H:8]1[C@@H:7]([CH2:24][O:25][C:26](=[O:28])[CH3:27])[O:6][CH:5]2[CH:10]([N:11]=[C:12]([NH:14][CH3:15])[S:13]2)[C@H:9]1[O:16][C:17](=[O:19])[CH3:18])(=[O:23])[CH3:22]

Participants

4

Reactant 2

HCID 24287Tin tetrachlorideHCID 86638171(2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-methylthioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate

Product 1

HCID 178482335HCID 178482335, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

(2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-methylthioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate (0.457 g, 1.09 mmol) was added to dry DCM, and SnCl4 (1.13 g, 4.33 mmol) was added dropwise. The reaction was stirred at room temperature overnight (16 h). The reaction was quenched with saturated aqueous NaHCO3 until the solution was basic and no more gas was evolved. The aqueous layer was extracted three times with DCM and the combined organic layers were dried with MgSO4, filtered and concentrated. The crude material was purified by flash chromatography (silica gel, EtOAc), providing (5R,6S,7R)-5-(acetoxymethyl)-2-(methylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diyl diacetate (22) as an oil (0.30 g, 77% yield). 1H NMR (500 MHz, CDCl3) δ 2.05 (s, 3H), 2.06 (s, 3H), 2.08 (s, 3H), 2.90 (s, 3H), 3.84 (m, 1H), 4.12 (m, 2H), 4.34 (dd, 1H, J=4.3, 6.2 Hz), 4.90 (ddd, 1H, J=0.8, 2.8, 9.6 Hz), 5.39 (dd, 1H, J=2.9, 4.1 Hz), 6.21 (d, 1H, J=6.5 Hz). 13 C NMR (125 MHz, CDCl3) δ 21.00, 21.10, 21.23, 31.19, 63.40, 68.67, 69.40, 72.24, 73.01, 90.03, 161.21, 169.72, 169.90, 170.89.

Workup

  1. additionwas added dropwise
  2. customThe reaction was quenched with saturated aqueous NaHCO3 until the solution
  3. extractionThe aqueous layer was extracted three times with DCM
  4. dry with materialthe combined organic layers were dried with MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude material was purified by flash chromatography (silica gel, EtOAc)

Sources & evidence

ORD record
ord-19af01ad02ac4166954a9ca81ba32fc0
Source dataset
uspto-grants-2012_12
Patent number
US08334310B2

Reaction notes

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