Boron Trichloride → HCID 131736721, compound

HRID 1483181Notes

Reaction equation

HRID 1483181 reaction equation
[CH2:1]([C:40]1[CH:45]=[CH:44][C:43]([CH2:46][C:47]23[C:57](=[O:58])[N:56]([CH3:59])[C:51]([CH2:60][O:61]CC4C=CC=CC=4)([C:52](=[O:55])[N:53]2[CH3:54])[S:50][CH:49]([C:69]2[CH:74]=[CH:73][C:72]([O:75][CH3:76])=[CH:71][CH:70]=2)[S:48]3)=[CH:42][CH:41]=1)[CH2:2][C:3]1[CH:8]=[CH:7][C:6]([CH2:9][C:10]23[C:20](=[O:21])[N:19]([CH3:22])[C:14]([CH2:23][O:24]CC4C=CC=CC=4)([C:15](=[O:18])[N:16]2[CH3:17])[S:13][CH:12]([C:32]2[CH:37]=[CH:36][C:35]([O:38][CH3:39])=[CH:34][CH:33]=2)[S:11]3)=[CH:5][CH:4]=1.B(Cl)(Cl)Cl>ClCCl>[CH2:2]([C:3]1[CH:8]=[CH:7][C:6]([CH2:9][C:10]23[C:20](=[O:21])[N:19]([CH3:22])[C:14]([CH2:23][OH:24])([C:15](=[O:18])[N:16]2[CH3:17])[S:13][CH:12]([C:32]2[CH:37]=[CH:36][C:35]([O:38][CH3:39])=[CH:34][CH:33]=2)[S:11]3)=[CH:5][CH:4]=1)[CH2:1][C:40]1[CH:45]=[CH:44][C:43]([CH2:46][C:47]23[C:57](=[O:58])[N:56]([CH3:59])[C:51]([CH2:60][OH:61])([C:52](=[O:55])[N:53]2[CH3:54])[S:50][CH:49]([C:69]2[CH:70]=[CH:71][C:72]([O:75][CH3:76])=[CH:73][CH:74]=2)[S:48]3)=[CH:42][CH:41]=1

Participants

4

Reactant 2

HCID 25135Boron TrichlorideHCID 131736722HCID 131736722, compound

Product 1

HCID 131736721HCID 131736721, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To an ice-cooled solution of 21 (125 mg, 0.126 mmol, 1 eq.) in dichloromethane, a 1 M solution of boron trichloride in dichloromethane (320 μL, 0.32 mmol, 2.5 eq) was added dropwise while stirring. The mixture was allowed to stand at 0° C. for 15 min and then was poured into the ice-cold water. The aqueous layer was extracted. with dichloromethane (3×50 mL). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. The crude reaction mixture was purified by flash column chromatography to give 78 mg of product mixture of meso-22 and (±)-22 as a white solid (75% combined yield). The mixture of meso-22 and (±)-22 was further purified on silica gel column using gradient of EtOAC in dichloromethane from 10% to 50% in order to separate meso-22 and (±)-22. Analytical data for (±)-22: 1H NMR (CDCl3, ppm) δ: 7.32 (d, 4H), 6.93 (d, 4H) 6.89 (d, 4H), 6.86 (d, 4H), 5.08 (s, 2H), 4.47 (dd, J=6 Hz, 13 Hz, 2H), 4.37 (d, 2H), 4.26 (m, 2H), 3.98 (dd, J 10 Hz, 13 Hz, 2H), 3.80 (s, 6H), 3.41 (s, 6H), 2.98 (d, 2H), 2.84 (s, 6H), 2.69 (d, 2H). 13C NMR (DMSO-d6, ppm) δ:165.42, 165.19, 160.06, 140.00, 132.93, 130.52, 128.53, 128.42, 126.82, 114.38, 73.47, 71.51, 60.79, 55.29, 49.91, 40.14, 36.36, 29.60, 27.96. FABMS: Calcd. for C46H50N4O8S4: 914.3. Found [M+Na]+: 936.9. Analytical data for meso-7: 1H NMR (CDCl3, ppm) δ: 7.33 (d, 4H), 7.02 (d, 4H) 6.99 (d, 4H), 6.86 (d, 4H), 5.09 (s, 2H), 4.35 (dd, J=10 Hz, 13 Hz, 2H), 4.37 (d, 2H), 3.11 (m, 2H), 4.04 (dd, J=10 Hz, 13 Hz, 2H), 3.81 (s, 6H), 3.41 (s, 6H), 2.91 (s, 6H), 2.85 (s, 4H). 13C NMR (DMSO-d6, ppm) δ:165.47, 165.24, 160.10, 140.04, 132.96, 130.56, 128.55, 128.48, 126.85, 114.42, 73.50, 71.55, 60.83, 55.34, 49.96, 40.14, 36.42, 29.63, 28.00. FABMS: Calcd. for C46H50N4O8S4: 914.3. Found [M+Na]+: 936.9.

Workup

  1. extractionThe aqueous layer was extracted
  2. dry with materialThe combined organic extracts were dried over anhydrous magnesium sulfate
  3. filtrationfiltered
  4. customevaporated under reduced pressure
  5. customThe crude reaction mixture
  6. customwas purified by flash column chromatography
  7. customto give
  8. customas a white solid (75% combined yield)
  9. additionThe mixture of meso-22 and (±)-22
  10. customwas further purified on silica gel column
  11. customto separate meso-22 and (±)-22

Sources & evidence

ORD record
ord-c78b0389b85c4257812a5c6659864018
Source dataset
uspto-grants-2016_08
Patent number
US09416145B2

Reaction notes

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