Bromochloromethane → HCID 86740164, compound

HRID 2206314Notes

Reaction equation

HRID 2206314 reaction equation
C([Li])CCC.C1([B:12]([OH:14])[OH:13])C=CC=CC=1.[C:15]12([OH:26])[CH2:23][CH:19]([C:20]1([CH3:22])[CH3:21])[CH2:18][CH2:17][C:16]2([OH:25])[CH3:24].BrCCl>C1COCC1>[C:15]1([CH2:23][B:12]([OH:14])[OH:13])[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.[C:15]12([OH:26])[CH2:23][CH:19]([C:20]1([CH3:22])[CH3:21])[CH2:18][CH2:17][C:16]2([OH:25])[CH3:24]

Participants

5

Reactant 3

HCID 6333BromochloromethaneHCID 131735850HCID 131735850, compoundHCID 178418339Butyllithium

Product 1

HCID 86740164HCID 86740164, compoundYield 156.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

n-Butyllithium (2.5 M soln in hexane, 4.66 mL, 11.64 mmol) was added dropwise to a stirred solution of (+)-pinanediol benzeneboronate 12a (Morandi, F. et al., J. Am. Chem. Soc. 2003, 125, 685-695) (2.48 g, 9.70 mmol) and bromochloromethane (0.95 mL, 14.55 mmol) in THF (25 mL) at −80° C. under argon atmosphere. The mixture was allowed to reach room temperature overnight. Then the solution was partitioned between light petroleum (80 mL) and water (25 mL), the organic phase was washed with saturated ammonium chloride (20 mL) and the combined aqueous phases were extracted with petroleum ether (2×40 mL). The organic phases were dried, filtered and concentrated and the crude residue was purified by gradient chromatography (light petroleum to light petroleum/ethyl ether 95:5), affording 13a as a colorless oil (2.33 g, 89% yield). [α]D+14.2 (c 2.0, CHCl3). 1H-NMR (200 MHz, CDCl3): δ 0.87 (3H, s, pinanyl CH3), 1.10 (1H, d, J 10.8, pinanyl Hendo), 1.30 (3H, s, pinanyl CH3), 1.41 (3H, s, pinanyl CH3), 1.62-2.39 (5H, m, pinanyl protons), 2.37 (2H, s, BCH2), 4.30 (1H, dd, J 8.8, 1.9, CHOB), 7.10-7.31 (5H, m, HAr). 13C-NMR (50 MHz, CDCl3): δ 19.3 (CB), 24.0, 26.4, 27.1, 28.6, 35.5, 38.1, 39.5, 51.3, 78.0, 85.8, 124.8, 128.3, 128.9, 138.8. EI-MS: m/z 217 (M++1, 2%), 270 (M+, 81%), 269 (M+−1, 21%), 255 (32), 229 (24), 214 (32), 201 (88), 200 (33), 187 (30), 179 (28), 174 (100), 135 (58), 134 (38), 119 (32), 118 (26), 117 (28), 109 (24), 93 (44), 91 (74), 83 (75), 82 (32), 81 (34), 79 (24), 77 (26), 67 (66), 65 (27), 55 (47), 53 (29). Anal. Calcd. for C17H23BO2: C, 75.57; H, 8.58. Found: C, 75.39; H, 8.44.

Workup

  1. customThen the solution was partitioned between light petroleum (80 mL) and water (25 mL)
  2. washthe organic phase was washed with saturated ammonium chloride (20 mL)
  3. extractionthe combined aqueous phases were extracted with petroleum ether (2×40 mL)
  4. customThe organic phases were dried
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customthe crude residue was purified by gradient chromatography (light petroleum to light petroleum/ethyl ether 95:5)

Sources & evidence

ORD record
ord-8c082c2cad9a410a90d9f741385a3fac
Source dataset
uspto-grants-2016_06
Patent number
US09371337B2

Reaction notes

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