Allyl bromide → HCID 54286954, compound
Reaction equation
N([Si:4]([CH3:7])([CH3:6])[CH3:5])=[N+]=[N-].[CH:8]12[O:15][CH:9]1[CH2:10][CH2:11][CH2:12][CH2:13][CH2:14]2.C([Br:19])C=C>ClC1C=CC=CC=1>[Br:19][C@@H:8]1[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][C@H:9]1[O:15][Si:4]([CH3:7])([CH3:6])[CH3:5]Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Procedure
To a vial containing 0.03 grams of (R)-catalyst prepared as in Example 1 was added a solution of azidotrimethylsilane (0.34 g, 2.95 mmol) and cycloheptene oxide (0.28 g, 2.50 mmol) in a mixture of allyl bromide (4.0 mL) and chlorobenzene (4.0 ml). After 48 h the volatiles were removed at reduced pressure and the residue was purified by flash chromatography on 220-400 mesh silica with 98% hexane and 2% ether as eluant. The product (1R,2R)-1-bromo-2-trimethylsiloxycycloheptane (0.54 g, 82%) was isolated by distillation of the solvent at reduced pressure. Anal. for C10H21OSiBr. Calcd: C, 45.28; H, 7.98; Br. 30.12; found: C, 45.26; H, 8.12; Br 30.55. 1H NMR: d 0.17 (s, 9 H), 1.45-1.89 (m, 8 H), 2.03 (M, 1 H), 2.28 (m, 1 H), 4.01 (m, 1 H), 4.12 (m, 1 H). 13C NMR: d 0.33, 21.62, 24.26, 27.49, 33.78, 34.13, 62.41, 78.90. [a]D25=−28.2, c=1.24 g/100 mL chloroform. Chiral capillary gas chromatographic analysis at 120° C. on Cyclodex B stationary phase indicated that the enantiomeric excess of the product was 80%.
Workup
- additionTo a vial containing
- custom0.03 grams of (R)-catalyst prepared as in Example 1
- customAfter 48 h the volatiles were removed at reduced pressure
- customthe residue was purified by flash chromatography on 220-400 mesh silica with 98% hexane and 2% ether as eluant
Sources & evidence
- ORD record
- ord-7a438395e94f440299d54e515d1ef991
- Source dataset
- uspto-grants-2001_03
- Patent number
- US06207847B1
Reaction notes
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