Dichloromethane → HCID 86587083, compound

HRID 1244740Notes

Reaction equation

HRID 1244740 reaction equation
[CH2:1]([Cl:3])Cl.[Li]CCCC.C(OC([B:19]([OH:21])[OH:20])C)C1C=CC=CC=1.[C:22]12([OH:33])[CH2:30][CH:26]([C:27]1([CH3:29])[CH3:28])[CH2:25][CH2:24][C:23]2([OH:32])[CH3:31].C1C[O:37][CH2:36][CH2:35]1>CCOCC.[Cl-].[Zn+2].[Cl-]>[CH2:27]([O:37][CH:36]([CH3:35])[CH:1]([B:19]([OH:21])[OH:20])[Cl:3])[C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:30]=1.[C:22]12([OH:33])[CH2:30][CH:26]([C:27]1([CH3:29])[CH3:28])[CH2:25][CH2:24][C:23]2([OH:32])[CH3:31]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 8028Tetrahydrofuran2×HCID 70130035HCID 70130035, compoundHCID 178418339Butyllithium

Product 1

HCID 86587083HCID 86587083, compoundYield 51%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 3283Diethyl EtherSolvent

Conditions

Temperature
-100 °C

Procedure

CH2Cl2 (0.80 mL, 12.7 mmol) was added to THF (40 mL) and cooled to −100° C. n-BuLi (1.6 N, 6.3 mL) was slowly added while maintaining a temperature of −100° C. The flask was stirred at −100° C. for an additional 45 min. Pinanediol (1-benzyloxyethyl)boronate (2.66 g, 8.46 mmol), dissolved in THF (20 mL), was added followed by a solution of zinc(II) chloride in ether (1.0 N, 17 mL). The THF was evaporated and the residue was redissolved in hexanes (150 mL). The solution was washed with saturated aqueous ammonium chloride, brine, and dried over MgSO4. It was concentrated to give a light oil. This oil was purified by silica gel column chromatography (10% ethyl acetate/90% hexanes eluant) to yield 1.55 g (51%) of a clear oil. 1H-NMR (CDCl3)δ 7.36 (m, 5H), 4.58 (m, 2H), 4.37 (d, 1H), 3.91 (m, 1H), 3.56 (d, 2H), 2.39-1.81 (m, 6H), 1.40 (d, 3H), 1.34 (d, 3H), 1.29 (s, 3H), 0.84 (s, 3H).

Workup

  1. additionwas slowly added
  2. additionwas added
  3. customThe THF was evaporated
  4. dissolutionthe residue was redissolved in hexanes (150 mL)
  5. washThe solution was washed with saturated aqueous ammonium chloride, brine
  6. dry with materialdried over MgSO4
  7. concentrationIt was concentrated
  8. customto give a light oil
  9. customThis oil was purified by silica gel column chromatography (10% ethyl acetate/90% hexanes eluant)

Sources & evidence

ORD record
ord-07f4cf118d574ce398898cfb7a6ca050
Source dataset
uspto-grants-2006_10
Patent number
US07122627B2

Reaction notes

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