Trichloro(dimethylsulfonio)boranuide → (3aR,4R,5R,6R,7aS)-6-(hydroxymethyl)-2-(pyrrolidin-1-yl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazole-4,5-diol

HRID 2274311Notes

Reaction equation

HRID 2274311 reaction equation
C([O:8][C@@H:9]1[C@H:14]2[N:15]=[C:16]([N:18]3[CH2:22][CH2:21][CH2:20][CH2:19]3)[S:17][C@H:13]2[CH2:12][C@H:11]([CH2:23][O:24]CC2C=CC=CC=2)[C@H:10]1[O:32]CC1C=CC=CC=1)C1C=CC=CC=1.[B-](Cl)(Cl)(Cl)[S+](C)C>>[OH:24][CH2:23][C@@H:11]1[C@@H:10]([OH:32])[C@H:9]([OH:8])[C@H:14]2[N:15]=[C:16]([N:18]3[CH2:22][CH2:21][CH2:20][CH2:19]3)[S:17][C@H:13]2[CH2:12]1

Participants

3

Reactant 2

HCID 16211690Trichloro(dimethylsulfonio)boranuideHCID 67480335(3aR,4R,5R,6R,7aS)-4,5-Bis(benzyloxy)-6-((benzyloxy)methyl)-2-(pyrrolidin-1-yl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazole

Product 1

HCID 67480457(3aR,4R,5R,6R,7aS)-6-(hydroxymethyl)-2-(pyrrolidin-1-yl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazole-4,5-diol

Procedure

To a solution of (3aR,4R,5R,6R,7aS)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-2-(pyrrolidin-1-yl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazole (0.200 g, 0.369 mmol) was added excess boron trichloride-methyl sulfide complex (1.70 g, 9.48 mmol). The mixture was stirred at room temperature for 4 days, and then quenched with MeOH at 0° C. The quenched solution was stirred for 10 min, and then concentrated under reduced pressure to dryness. The residue was purified on silica gel by flash column chromatography (1.0 M NH3 in MeOH/CH2Cl2, 1:4), affording (3aR,4R,5R,6R,7aS)-6-(hydroxymethyl)-2-(pyrrolidin-1-yl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazole-4,5-diol an off-white solid (0.058 g, 58%). 1H NMR (400 MHz, CD3OD) 4.35-4.33 (m, 1H), 3.79 (dd, J=4.1, 10.4 Hz, 1H), 4.74 (dd, J=6.1, 8.6 Hz, 1H), 3.63 (dd, J=6.1, 10.4 Hz, 1H), 3.50-3.46 (m, 2H), 3.44-3.30 (m, 3H), 3.22 (t, J=10.4, 1H), 2.23-2.18 (m, 1H), 1.98-1.91 (m, 5H), 1.78-1.61 (m, 1H); 13C NMR (100 MHz, CD3OD) δ 164.62, 78.45, 76.43, 74.37, 64.12, 54.72, 50.27, 40.73, 26.90, 26.44; MS, m/z=273 (M+1).

Workup

  1. customquenched with MeOH at 0° C
  2. stirringThe quenched solution was stirred for 10 min
  3. concentrationconcentrated under reduced pressure to dryness
  4. customThe residue was purified on silica gel by flash column chromatography (1.0 M NH3 in MeOH/CH2Cl2, 1:4)

Sources & evidence

ORD record
ord-a39c2496efaa445996b023885fc6d201
Source dataset
uspto-grants-2015_09
Patent number
US09126957B2

Reaction notes

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