Boron trifluoride etherate → HCID 86659939, compound

HRID 338555Notes

Reaction equation

HRID 338555 reaction equation
B(F)(F)F.CCOCC.[CH2:10]([O:17][C@H:18]1[C@@H:23]([N:24]=[N+:25]=[N-:26])[C@@H:22]([CH2:27][O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[O:21][CH:20]=[CH:19]1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[C:36]([OH:39])(=[O:38])[CH3:37].[C:40]([OH:43])(=[O:42])[CH3:41].IC1C=CC=CC=1.C(N(CC)CC)C>ClCCl>[C:36]([O:39][C@@H:19]1[C@@H:18]([O:17][CH2:10][C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=2)[C@@H:23]([N:24]=[N+:25]=[N-:26])[C@@H:22]([CH2:27][O:28][CH2:29][C:30]2[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=2)[O:21][C@H:20]1[O:43][C:40](=[O:42])[CH3:41])(=[O:38])[CH3:37]

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 8471TriethylamineHCID 12217721Iodo benzene diacetateHCID 86659940HCID 86659940, compound

Product 1

HCID 86659939HCID 86659939, compoundYield 85.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Boron trifluoride diethyl etherate (74.0 μL, 0.636 mmol, 0.219 equiv) was added to a solution of glycal 218 (1.020 g, 2.904 mmol, 1.000 equiv) and iodobenzene diacetate (1.119 g, 3.474 mmol, 1.196 equiv) in dichloromethane (36 mL) in a cold bath at −50° C. After 25 min, the yellow solution was transferred to a cold bath at −25° C. and stirred for an additional 30 min. Triethyl amine (2.0 mL) was added, and the resulting suspension was diluted with dichloromethane (20 mL) and washed with saturated aqueous sodium bicarbonate solution (30 mL). The aqueous layer was extracted with dichloromethane (30 mL), and the combined organic layers were dried with magnesium sulfate and purified by silica gel chromatography (hexane/ethyl acetate 4:1 to 3:1) to afford 222 (1.163 g, 2.477 mmol, 85% yield) as a yellow solid. Rf=0.25 (hexane/ethyl acetate 3:1); 1H NMR (400 MHz, CDCl3) δ 7.41-7.28 (m, 10H), 5.51 (d, J=8.3, 1H), 5.30 (dd, J=9.8, 8.4, 1H), 4.74 (d, J=12.2, 1H), 4.56 (d, J=12.3, 1H), 4.54 (s, 2H), 4.08 (dd, J=3.6, 1.1, 1H), 3.74 (td, J=6.7, 1.3, 1H), 3.69 (dd, J=9.8, 3.6, 1H), 3.63 (d, J=6.8, 2H), 2.06 (s, 3H), 2.00 (s, 3H); 13C NMR (126 MHz, CDCl3) δ 169.50, 169.38, 137.51, 137.25, 128.73, 128.69, 128.32, 128.23, 128.20, 127.92, 92.47, 78.73, 73.86, 72.60, 72.23, 69.78, 67.82, 59.10, 20.96, 20.88; FTIR (neat film) 2920.8, 2107.7, 1755.9, 1454.8, 1368.4, 1232.5, 1214.6, 1059.1, 739.3, 698.4 cm−1; HRMS (ESI) m/z: Calcd for C24H27N3O7Na (M+Na+) 492.1747. found 492.1755.

Workup

  1. customthe yellow solution was transferred to a cold bath at −25° C.
  2. washwashed with saturated aqueous sodium bicarbonate solution (30 mL)
  3. extractionThe aqueous layer was extracted with dichloromethane (30 mL)
  4. dry with materialthe combined organic layers were dried with magnesium sulfate
  5. custompurified by silica gel chromatography (hexane/ethyl acetate 4:1 to 3:1)

Sources & evidence

ORD record
ord-5a208a761f2d4b248183d9f0ab6a1c77
Source dataset
uspto-grants-2014_11
Patent number
US08889842B2

Reaction notes

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