Tin tetrachloride → (3aR,5R,6S,7R,7aR)-5-(acetoxymethyl)-2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diyl diacetate

HRID 1854238Notes

Reaction equation

HRID 1854238 reaction equation
C(O[C@H:5]1[C@H:10]([NH:11][C:12]([NH:14][C:15]([O:17][CH2:18][CH:19]2[C:31]3[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=3[C:25]3[C:20]2=[CH:21][CH:22]=[CH:23][CH:24]=3)=[O:16])=[S:13])[C@@H:9]([O:32][C:33](=[O:35])[CH3:34])[C@H:8]([O:36][C:37](=[O:39])[CH3:38])[C@@H:7]([CH2:40][O:41][C:42](=[O:44])[CH3:43])[O:6]1)(=O)C.Cl[Sn](Cl)(Cl)Cl.C([O-])(O)=O.[Na+]>C(Cl)Cl>[C:37]([O:36][C@@H:8]1[C@@H:7]([CH2:40][O:41][C:42](=[O:44])[CH3:43])[O:6][C@H:5]2[C@H:10]([N:11]=[C:12]([NH:14][C:15]([O:17][CH2:18][CH:19]3[C:31]4[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=4[C:25]4[C:20]3=[CH:21][CH:22]=[CH:23][CH:24]=4)=[O:16])[S:13]2)[C@H:9]1[O:32][C:33](=[O:35])[CH3:34])(=[O:39])[CH3:38]

Participants

5

Reactant 3

HCID 24287Tin tetrachlorideHCID 516892Sodium BicarbonateHCID 86638169(2S,3R,4R,5S,6R)-6-(acetoxymethyl)-3-(3-(((9H-fluoren-9-yl)methoxy)carbonyl)thioureido)-tetrahydro-2H-pyran-2,4,5-triyl triacetate

Product 1

HCID 86638170(3aR,5R,6S,7R,7aR)-5-(acetoxymethyl)-2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diyl diacetateYield 69%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

The thiourea from above (200 mg, 0.32 mmol) was dissolved in CH2Cl2 (4 mL) and SnCl4 (0.5 mL, 4.0 mmol) was added. Then the resulting mixture was stirred at room temperature for 16 h. The solution was diluted saturated aqueous NaHCO3 (20 mL), then the resulting mixture was extracted with CH2Cl2 (3×10 mL) and the combined organic extracts were dried (Na2SO4) and concentrated. Flash chromatography of the residue (EtOAc:hexanes 2:3) gave (3aR,5R,6S,7R,7aR)-5-(acetoxymethyl)-2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diyl diacetate as a pale colourless foam (125 mg, 69% yield). 1H NMR 500 MHz, CDCl3) δ 1.88 (s, 3H), 2.04 (s, 3H), 2.12 (s, 3H), 3.69 (m, 1H), 3.81 (ddd, 1H, J=2.5, 5.5, 6.5 Hz), 4.12 (dd, 1H, J=2.5, 12.5 Hz), 4.21-4.26 (m, 2H), 4.55 (dd, 1H, J=6.0, 12.5 Hz), 4.72-4.75 (dd, 1H, J=6.5, 6.5 Hz), 4.95 (dd, 1H J=5.5, 9.5 Hz), 5.24 (dd, 1H J=6.5, 9.5 Hz), 6.01 (d, 1H, J=6.5 Hz), 7.35 (dd, 2H, J=7.1, 7.8 Hz), 7.44 (dd, 2H, J=7.0, 7.8 Hz), 7.59 (d, 2H, J=7.1 Hz), 7.81 (d, 2H, J=7.0 Hz). 13C NMR (125 MHz, CDCl3) δ 20.62, 20.71, 21.35, 46.78, 57.91, 63.70, 67.92, 69.46, 71.88, 72.52, 90.23, 120.71, 120.89, 123.83, 124.04, 125.15, 127.76, 127.97, 129.61, 129.72, 130.08, 141.31, 142.86, 152.11, 161.43, 169.11, 169.63, 170.23.

Workup

  1. extractionthe resulting mixture was extracted with CH2Cl2 (3×10 mL)
  2. dry with materialthe combined organic extracts were dried (Na2SO4)
  3. concentrationconcentrated

Sources & evidence

ORD record
ord-e37196565d824955b5e1931d042514c4
Source dataset
uspto-grants-2015_02
Patent number
US08962664B2

Reaction notes

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