Hydrochloric Acid → (2-Fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)trimethylsilane

HRID 516540

Reaction equation

C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][C:10]([Si:13]([CH3:16])([CH3:15])[CH3:14])=[C:9]([F:17])[CH:8]=1.C(O[B:22]1[O:26][C:25]([CH3:28])([CH3:27])[C:24]([CH3:30])([CH3:29])[O:23]1)(C)C.C(=O)=O.CC(C)=O.Cl>O1CCCC1.O>[F:17][C:9]1[CH:8]=[C:7]([B:22]2[O:26][C:25]([CH3:28])([CH3:27])[C:24]([CH3:30])([CH3:29])[O:23]2)[CH:12]=[CH:11][C:10]=1[Si:13]([CH3:16])([CH3:15])[CH3:14]

Participants

Conditions

Temperature: -78 °C

Procedure

A 2.5 M solution of n-butyllithium (8.5 mL, 21 mmol, 1.1 equiv) was added to a stirred solution of (4-bromo-2-fluorophenyl)trimethylsilane (4.8 g, 19 mmol, 1.0 equiv) in tetrahydrofuran (80 mL) at −78° C. The resulting orange solution was stirred at −78° C. for 15 m. 2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.4 mL, 21 mmol, 1.1 equiv) was added and the cloudy orange solution was allowed to slowly warm to 23° C., by allowing the dry ice/acetone bath to melt, and stirred for 20 h. The reaction mixture was diluted with water (200 mL), adjusted to approximately pH 4 using 1M hydrochloric acid, and extracted with dichloromethane (3×100 mL). The combined organic layers were dried (magnesium sulfate), gravity filtered, and concentrated by rotary evaporation to afford the title compound as a pale yellow semisolid (6.0 g, 99%): 1H NMR (400 MHz, CDCl3) δ 7.55 (dt, J=7.5, 1 Hz, 1H), 7.38-7.42 (m, 2H), 1.34 (s, 12H), 0.29 (d, J=1 Hz, 9H).

Workup

temperatureto slowly warm to 23° C.
stirringstirred for 20 h
extractionextracted with dichloromethane (3×100 mL)
dry with materialThe combined organic layers were dried (magnesium sulfate), gravity
filtrationfiltered
concentrationconcentrated by rotary evaporation

Sources & evidence

ORD record: ord-2049a3cdbf0442de828f8ddfdc905431
Source dataset: uspto-grants-2015_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09113629B2

Linked notes

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