p-Toluenesulfonic acid → 5-chloro-4-(4-ethylbenzyl)-2-((2S,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)-2-(2-methylprop-1-enyl)tetrahydro-2H-pyran-2-yl)phenol

HRID 1713593Notes

Reaction equation

HRID 1713593 reaction equation
C1(C)C=CC(S(O)(=O)=O)=CC=1.[Cl:12][C:13]1[C:14]([CH2:63][C:64]2[CH:69]=[CH:68][C:67]([CH2:70][CH3:71])=[CH:66][CH:65]=2)=[CH:15][C:16]([C@@:20]2([CH2:59][C:60]([CH3:62])=[CH2:61])[C@H:25]([O:26][CH2:27][C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C@@H:24]([O:34][CH2:35][C:36]3[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=3)[C@H:23]([O:42][CH2:43][C:44]3[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=3)[C@@H:22]([CH2:50][O:51][CH2:52][C:53]3[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=3)[O:21]2)=[C:17]([OH:19])[CH:18]=1>>[Cl:12][C:13]1[C:14]([CH2:63][C:64]2[CH:69]=[CH:68][C:67]([CH2:70][CH3:71])=[CH:66][CH:65]=2)=[CH:15][C:16]([C@@:20]2([CH:59]=[C:60]([CH3:62])[CH3:61])[C@H:25]([O:26][CH2:27][C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=3)[C@@H:24]([O:34][CH2:35][C:36]3[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=3)[C@H:23]([O:42][CH2:43][C:44]3[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=3)[C@@H:22]([CH2:50][O:51][CH2:52][C:53]3[CH:54]=[CH:55][CH:56]=[CH:57][CH:58]=3)[O:21]2)=[C:17]([OH:19])[CH:18]=1

Participants

3

Reactant 2

HCID 6101p-Toluenesulfonic acidHCID 687926765-chloro-4-(4-ethylbenzyl)-2-((2S,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)-2-(2-methylallyl)tetrahydro-2H-pyran-2-yl)phenol

Product 1

HCID 687901645-chloro-4-(4-ethylbenzyl)-2-((2S,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(benzyloxymethyl)-2-(2-methylprop-1-enyl)tetrahydro-2H-pyran-2-yl)phenolYield 75.4%

Conditions

Temperature
65 °C

Procedure

A mixture of p-toluenesulfonic acid (0.136 mg, 0.789 mmol) and 25 (0.65 g, 0.789 mmol) was heated at 65° C. for 7 hours. The reaction mixture was cooled to ambient temperature, after which it was partitioned between 10% NaHCO3 and EtOAc. The organic layer was dried (Na2SO4), filtered, and evaporated. The residue was purified by silica gel column chromatography eluting with 5% EtOAc in petroleum ether to give 26 (490 mg, 75%). 1H NMR (300 MHz, CDCl3) δ 8.83 (s, 1H), 7.20-7.34 (m, 18H), 7.03-7.10 (m, 2H), 6.92-7.00 (m, 7H), 6.85 (s, 1H), 5.59 (s, 1H), 4.77-4.89 (m, 3H), 4.63 (d, J=12.0 Hz, 1H), 4.36-4.44 (m, 3H), 4.00 (d, J=15.6 Hz, 1H), 3.95 (dd, J=5.1, 10.2 Hz, 1H), 3.65-3.80 (m, 6H), 3.52 (dd, J=2.1, 10.5 Hz, 1H), 2.56 (q, J=7.8 Hz, 2H), 1.70 (s, 3H), 1.42 (s, 3H), 1.19 (t, J=7.5 Hz, 3H). LC/MS m/z 846 (M+Na).

Workup

  1. temperatureThe reaction mixture was cooled to ambient temperature
  2. customafter which it was partitioned between 10% NaHCO3 and EtOAc
  3. dry with materialThe organic layer was dried (Na2SO4)
  4. filtrationfiltered
  5. customevaporated
  6. customThe residue was purified by silica gel column chromatography
  7. washeluting with 5% EtOAc in petroleum ether

Sources & evidence

ORD record
ord-dab09be385a349a3b9ced24009df1545
Source dataset
uspto-grants-2010_09
Patent number
US07795228B2

Reaction notes

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