Boron trichloride methyl sulfide → (3aR,4R,5R,6R,7aS)-2-(dimethylamino)-6-(hydroxymethyl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazole-4,5-diol

HRID 2274313Notes

Reaction equation

HRID 2274313 reaction equation
B(Cl)(Cl)Cl.CSC.[CH3:8][N:9]([CH3:45])[C:10]1[S:11][C@H:12]2[CH2:18][C@H:17]([CH2:19][O:20]OCC3C=CC=CC=3)[C@@H:16]([O:29]CC3C=CC=CC=3)[C@H:15]([O:37]CC3C=CC=CC=3)[C@H:13]2[N:14]=1>>[CH3:8][N:9]([CH3:45])[C:10]1[S:11][C@H:12]2[CH2:18][C@H:17]([CH2:19][OH:20])[C@@H:16]([OH:29])[C@H:15]([OH:37])[C@H:13]2[N:14]=1

Participants

3

Reactant 2

HCID 10899259Boron trichloride methyl sulfideHCID 86727205(3aR,4R,5R,6R,7aS)-2-(dimethylamino)-4,5-bisbenzyloxy-6-(benzyloxyoxymethyl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazole

Product 1

HCID 67480579(3aR,4R,5R,6R,7aS)-2-(dimethylamino)-6-(hydroxymethyl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazole-4,5-diolYield 37.3%

Procedure

Prepared by boron trichloride-methyl sulfide de-benzylation via a procedure as described above in Intermediate Example 4 Step 3 from (3aR,4R,5R,6R,7aS)-2-(dimethylamino)-4,5-bisbenzyloxy-6-(benzyloxyoxymethyl)-3a,4,5,6,7,7a-hexahydrobenzo[d]thiazole (0.270 g, 0.523 mmol). Purification on silica gel by flash column chromatography (1.0 M NH3 in MeOH/CH2Cl2, 1:4), afforded the product as an off-white solid (0.048 g, 36%). 1H NMR (400 MHz, CD3OD) δ 4.36-4.33 (m, 1H), 3.81-3.76 (m, 2H), 3.63 (dd, J=6.3, 10.8 Hz, 1H), 3.41 (t, J=9.1 Hz, 1H), 3.31 (t, J=9.8 Hz, 1H), 3.02 (s, 6H), 2.24-2.19 (m, 1H), 1.97-1.93 (m, 1H), 1.79-1.71 (m, 1H); 13C NMR (100 MHz, CD3OD) δ 171.90, 77.01, 73.49, 70.83, 63.54, 52.60, 41.98, 40.84, 26.53; MS, m/z=269 (M+23).

Workup

  1. customPurification on silica gel by flash column chromatography (1.0 M NH3 in MeOH/CH2Cl2, 1:4)

Sources & evidence

ORD record
ord-1906b32f9026494694c798ebed62dbd2
Source dataset
uspto-grants-2015_09
Patent number
US09126957B2

Reaction notes

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