Dichloromethane → HCID 53466556, compound

HRID 2261899Notes

Reaction equation

HRID 2261899 reaction equation
[C:1]([N:8]1[CH2:14][CH2:13][CH2:12][C@@H:9]1[CH:10]=O)([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].C[Si](C)(C)[N-][Si](C)(C)C.[Li+].C(Cl)Cl.[CH:28]1C=C2C(C(O)(O)C(=O)C2=C[CH:29]=1)=O>O1CCCC1.[Br-].C([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)C.CO>[C:4]([O:3][C:1]([N:8]1[CH2:14][CH2:13][CH2:12][C@@H:9]1/[CH:10]=[CH:28]\[CH3:29])=[O:2])([CH3:7])([CH3:6])[CH3:5]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 10236NinhydrinHCID 2733832Lithium HexamethyldisilazideHCID 7009153N-(tert-Butoxycarbonyl)-D-prolinal

Product 1

HCID 53466556HCID 53466556, compound

Reagents, catalysts & solvents 3

HCID 73727Phosphonium, ethyltriphenyl-, bromide (1:1)CatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of Boc-D-prolinal (0.5 g, 2.5 mmol) in tetrahydrofuran (10 mL) was added ethyltriphenylphosphonium bromide (3.7 g, 10.0 mmol) and cooled to −78° C. Then added dropwise lithium hexamethyldisilazide 1.0 M in THF (12 mL) and continued stirring from −78° C. to rt overnight. Upon completion as determined by TLC (99:1 methylene chloride to methanol with ninhydrin) the mixture was quenched with 20% ammonium chloride solution and extracted with ethyl acetate. The organic washed with brine, dried over sodium sulfate anhydrous and concentrated in vacuo very carefully as the product is volatile. Crude product was purified on silica gel using a 99:1 mixture of methylene chloride to methanol as mobile phase with ninhydrin to develop. Pure fractions were combined and dried to yield tert-butyl-(2R)-2-[(1Z)-prop-1-enyl]pyrrolidine-1-carboxylate. LC-MS m/z (minus t-butyl+1)=156. 1H NMR (CD3OD, 400 Mhz) 5.47-5.41 ppm (m, 1H), 5.34-5.28 (m, 1H), 4.58-4.53 (m, 1H), 3.42-3.34 (m, 3H), 2.14-2.06 (m, 1H), 1.96-1.77 (m, 2H), 1.70-1.58 (m, 3H), 1.42 (s, 9H).

Workup

  1. customwas quenched with 20% ammonium chloride solution
  2. extractionextracted with ethyl acetate
  3. washThe organic washed with brine
  4. dry with materialdried over sodium sulfate anhydrous
  5. concentrationconcentrated in vacuo very carefully as the product
  6. customCrude product was purified on silica gel using
  7. additiona 99:1 mixture of methylene chloride to methanol as mobile phase with ninhydrin
  8. customdried

Sources & evidence

ORD record
ord-048eccb2c30745319f0ae2007483d297
Source dataset
uspto-grants-2010_12
Patent number
US07847100B2

Reaction notes

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