1-Bromo-4-((methylsulfonyl)methyl)benzene → 4,4,5,5-Tetramethyl-2-(4'-((methylsulfonyl)methyl)-[1,1'-biphenyl]-4-yl)-1,3,2-dioxaborolane

HRID 1050237Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([CH2:8][S:9]([CH3:12])(=[O:11])=[O:10])=[CH:4][CH:3]=1.[CH3:13][C:14]1([CH3:36])[C:18]([CH3:20])([CH3:19])[O:17][B:16]([C:21]2[CH:26]=[CH:25][C:24](B3OC(C)(C)C(C)(C)O3)=[CH:23][CH:22]=2)[O:15]1>C1COCC1.C(=O)([O-])[O-].[Ag+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:19][C:18]1([CH3:20])[C:14]([CH3:13])([CH3:36])[O:15][B:16]([C:21]2[CH:26]=[CH:25][C:24]([C:2]3[CH:7]=[CH:6][C:5]([CH2:8][S:9]([CH3:12])(=[O:11])=[O:10])=[CH:4][CH:3]=3)=[CH:23][CH:22]=2)[O:17]1

Participants

Conditions

Temperature: 80 °C

Procedure

1-bromo-4-((methylsulfonyl)methyl)benzene (1.5 g, 6.02 mmol), 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (4.97 g, 15.05 mmol), and silver carbonate (1.826 g, 6.62 mmol) were dissolved in THF (60.2 ml) and sparged with N2 for 15 min. Then Pd(PPh3)4 (0.348 g, 0.301 mmol) was added and the reaction was heated to 80° C. overnight. The reaction was then cooled to rt, filtered through Celite™ and concentrated in vacuo. The resulting residue was purified by column chromatography on a Biotage™ 50 g column by eluting with 5% to 50% EtOAc:Hex to yield the desired product. 1H NMR δ (ppm) 7.83 (d, 2H), 7.69 (d, 2H), 7.64 (d, 2H), 7.54 (d, 2H), 4.46 (s, 2H), 2.89 (s, 3H), 1.4 (12H).

Workup

customsparged with N2 for 15 min
temperatureThe reaction was then cooled to rt
filtrationfiltered through Celite™
concentrationconcentrated in vacuo
customThe resulting residue was purified by column chromatography on a Biotage™ 50 g column
washby eluting with 5% to 50% EtOAc

Sources & evidence

ORD record: ord-3ca29cbe1875486984f01544e6e6fc8e
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09382243B2

Reaction notes

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