Toluene → HCID 67960118, compound

Temperature

-20 °C

In a dry 40 mL vial with a septum cap, S-CBS catalyst, 1 M in toluene (3.98 mL, 3.98 mmol), 2.0 M borane-dimethyl sulfide in tetrahydrofuran (1.69 mL, 3.37 mmol), and 10 mL dry tetrahydrofuran were premixed. The premix was cooled to −20° C. in an acetonitrile/dry ice bath. A tetrahydrofuran solution of 5-(3-Bromo-propylidene)-5,11-dihydro-dibenzo[a,d]cyclohepten-10-one (6) (1.00 g, 3.06 mmol) which had been stored over molecular sieves was then added dropwise. The reaction was allowed to slowly come to room temperature over ˜90 minutes. When complete, the reaction was cooled to 0° C. and 1 mL methanol added to quench the reaction. After 15 minutes of further stirring, 1 mL saturated sodium bicarbonate was added. The reaction mixture was then evaporated and the residue is separated between water (50 mL) and dichloromethane (50 mL). The organic layer was then separated, evaporated, and the crude residue was purified by silica gel chromatography using a 5-25% hexanes:ethyl acetate gradient. 0.86 g (85%) (S)-5-(3-bromo-propylidene)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten-10-ol (7b) was obtained as a faintly yellow oil. ESI MS m/z 623.3 (2(M−H2O)+H)+. 1H NMR (CDCl3, 250 MHz): 7.48 (1H, d), 7.33-7.12 (7H, m), 5.91 (1H, t), 5.12-4.70 (1H, 2×m), 3.65 (1H, d), 3.44 (1H, t) 3.06 (1H, dd), 2.73 (2H, m), 1.61 (2H, m).

1. customIn a dry 40 mL vial with a septum cap
2. additionwas then added dropwise
3. temperatureWhen complete, the reaction was cooled to 0° C.
4. customto quench
5. customthe reaction
6. customThe reaction mixture was then evaporated
7. customthe residue is separated between water (50 mL) and dichloromethane (50 mL)
8. customThe organic layer was then separated
9. customevaporated
10. customthe crude residue was purified by silica gel chromatography

ORD record

ord-6b4499ac274144e0bf4eac92f9d8349d

Source dataset

uspto-grants-2015_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09090535B2