Diiodomethane → HCID 57822476, compound

HRID 1615914Notes

Reaction equation

HRID 1615914 reaction equation
[CH2:1]([Zn]CC)C.ICI.[CH3:9][C:10]1([CH3:31])[C:14]([CH3:16])([CH3:15])[O:13][B:12](/[CH:17]=[CH:18]/[CH2:19][NH:20][C:21](=[O:30])[O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[O:11]1>ClCCl>[CH3:16][C:14]1([CH3:15])[C:10]([CH3:31])([CH3:9])[O:11][B:12]([CH:17]2[CH2:1][CH:18]2[CH2:19][NH:20][C:21](=[O:30])[O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[O:13]1

Participants

5

Reactant 3

HCID 6346DiiodomethaneHCID 57822466HCID 57822466, compoundHCID 178418750HCID 178418750, compound

Product 1

HCID 57822476HCID 57822476, compoundYield 67.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-15 °C

Procedure

A solution of diethylzinc (7.57 mL, 7.57 mmol) in dichloromethane (10 mL) was stirred at −78° C. under nitrogen as a solution of diiodomethane (1.22 mL, 15.1 mmol) in dichloromethane (10 mL) was added. The resulting mixture was stirred at −15° C. under nitrogen for 1 h to give a white milky suspension. A solution of (E)-benzyl (3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl)carbamate (1.2 g, 3.78 mmol) in dichloromethane (10 mL) was added. The reaction mixture was stirred at rt for 1 h. and was then quenched with 1HCl. The dichloromethane layer was separated. The aqueous layer was extracted with dichloromethane (2×20 mL). The combined organic layers were washed with aqueous sodium bicarbonate (2×20 mL) and brine (20 mL), dried over magnesium sulfate, and concentrated. The residue was purified by silica gel chromatography using 0-30% EtOAc/hexane as the eluent to give benzyl ((2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclopropyl)methyl)carbamate as a colorless oil (0.84 g, 60%). 1H NMR (400 MHz, METHANOL-d4) d 7.42-7.22 (m, 5H), 5.07 (s, 2H), 3.12-2.84 (m, 2H), 1.20 (s, 12H), 1.17-1.12 (m, 1H), 0.71-0.60 (m, 1H), 0.58-0.44 (m, 1H), −0.28 (dt, J=9.5, 5.8 Hz, 1H). M+1=332.2.

Workup

  1. additionwas added
  2. customto give a white milky suspension
  3. stirringThe reaction mixture was stirred at rt for 1 h.
  4. customwas then quenched with 1HCl
  5. customThe dichloromethane layer was separated
  6. extractionThe aqueous layer was extracted with dichloromethane (2×20 mL)
  7. washThe combined organic layers were washed with aqueous sodium bicarbonate (2×20 mL) and brine (20 mL)
  8. dry with materialdried over magnesium sulfate
  9. concentrationconcentrated
  10. customThe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-a9fe3615824f40f289b3a1350b8a7752
Source dataset
uspto-grants-2014_07
Patent number
US08765767B2

Reaction notes

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