Diisobutylaluminum hydride → HCID 71061309, compound

HRID 1910999Notes

Reaction equation

HRID 1910999 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[CH2:11][CH2:10][CH2:9][C:8]([C:12](OC)=[O:13])=[CH:7][C:6]=2[CH:16]=1.CC(C[AlH]CC(C)C)C>C(OCC)C.C1COCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[CH2:11][CH2:10][CH2:9][C:8]([CH2:12][OH:13])=[CH:7][C:6]=2[CH:16]=1

Participants

5

Reactant 2

HCID 14487Diisobutylaluminum hydrideHCID 10826647HCID 10826647, compound

Product 1

HCID 71061309HCID 71061309, compoundYield 98%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of methyl 2-bromo-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate from step A4 (170 mg, 0.605 mmol) in diethyl ether (2 mL) and THF (1 mL) was added 1.0 M DIBAL-H/hexanes (0.726 mL, 0.726 mmol) at −78° C. The mixture was stirred at rt for 16 h. Another 0.726 mL portion of DIBAL-H was added at 0° C., and the mixture was stirred at rt for an additional 2 h. The reaction mixture was diluted with 50 mL of diethyl ether, quenched with water, and extracted with EtOAc (100 mL). The organic layer was dried over sodium sulfate, filtered, and concentrated to give (2-bromo-6,7-dihydro-5H-benzo[7]annulen-8-yl)methanol (150 mg, 0.593 mmol, 98% yield). 1H NMR (500 MHz, chloroform-d) δ 7.30 (s, 1H), 7.22 (dd, J=7.9, 1.8 Hz, 1H), 6.98 (d, J=7.9 Hz, 1H), 6.45 (s, 1H), 4.21 (br. s., 2H), 2.81-2.71 (m, 2H), 2.34 (t, J=6.4 Hz, 2H), 2.08-1.98 (m, 2H).

Workup

  1. stirringthe mixture was stirred at rt for an additional 2 h
  2. customquenched with water
  3. extractionextracted with EtOAc (100 mL)
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-7cde5d3d8d9040ef8c94fb1a9393ad49
Source dataset
uspto-grants-2013_12
Patent number
US08604024B2

Reaction notes

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