Boron tribromide → HCID 54456143, compound

HRID 2416702Notes

Reaction equation

HRID 2416702 reaction equation
B(Br)(Br)Br.C[O:6][C:7]1[CH:34]=[CH:33][C:10]2[CH2:11][C@@H:12]([CH2:28][C:29]([O:31][CH3:32])=[O:30])[C:13](=[O:27])[N:14]([CH2:16][C:17]3[CH:22]=[CH:21][C:20]([C:23]([F:26])([F:25])[F:24])=[CH:19][CH:18]=3)[CH2:15][C:9]=2[CH:8]=1>C(Cl)Cl>[OH:6][C:7]1[CH:34]=[CH:33][C:10]2[CH2:11][C@@H:12]([CH2:28][C:29]([O:31][CH3:32])=[O:30])[C:13](=[O:27])[N:14]([CH2:16][C:17]3[CH:18]=[CH:19][C:20]([C:23]([F:26])([F:24])[F:25])=[CH:21][CH:22]=3)[CH2:15][C:9]=2[CH:8]=1

Participants

4

Reactant 2

HCID 25134Boron tribromideHCID 53923993HCID 53923993, compound

Product 1

HCID 54456143HCID 54456143, compoundYield 92.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-5 °C

Procedure

A solution of boron tribromide in CH2Cl2 (1.0 M, 160 mL, 160 mmol) was added dropwise over 30 min to a solution of methyl (S)-8-methoxy-3-oxo-2-(4-trifluoromethylbenzyl)-2,3,4,5-tetrahydro-1H-2-benzazepine-4-acetate (16.67 g, 39.6 mmol) in anhydrous CH2Cl2 (150 mL) at −20° C. under argon. After an additional 1.5 hr at −15 to −20° C., the reaction was recooled to −20° C. and quenched by careful dropwise addition of MeOH (160 mL). The reaction was stirred at −10 to 0° C. for 1 hr, then was concentrated on the rotavap. The residue was reconcentrated from MeOH (2×). Purification by flash chromatography on silica gel (50 to 100% ethyl acetate/hexanes) gave the title compound (14.87 g, 92%) as a white solid: [α]D −81.8° (c, 1.0, MeOH); TLC (silica, 50% EtOAc/hexane) Rf 0.54; MS (ES) m/e 408.2 (M+H)+; 1H NMR (400, CDCl3+2% DMSO-d6) δ 7.53 (d, J=8.1 Hz, 2H), 7.31 (d, J=8.1 Hz, 2H), 6.93 (d, J=8.4 Hz, 1H), 6.70 (dd, 1H), 6.41 (d, J=2.3 Hz, 1H), 5.16 (d, J=16.4 Hz, 1H), 5.01 (d, J=15.6 Hz, 1H), 4.39 (d, J=15.6 Hz, 1H), 3.84 (m, 1H), 3.73 (d, J=16.4 Hz, 1H), 3.71 (s, 3H), 3.01 (dd, 1H), 2.98 (m, 1H), 2.90 (dd, 1H), 2.47 (dd, 1H).

Workup

  1. customwas recooled to −20° C.
  2. customquenched by careful dropwise addition of MeOH (160 mL)
  3. concentrationwas concentrated on the rotavap
  4. customPurification by flash chromatography on silica gel (50 to 100% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-d00b727509c146ff9a88fac18326729d
Source dataset
uspto-grants-2004_11
Patent number
US06825188B2

Reaction notes

Loading…