Sodium Acetate → 1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrrolo[2,3-b]pyridine

HRID 886619Notes

Reaction equation

Br[C:2]1[CH:3]=[C:4]2[CH:10]=[CH:9][N:8]([CH2:11][O:12][CH2:13][CH2:14][Si:15]([CH3:18])([CH3:17])[CH3:16])[C:5]2=[N:6][CH:7]=1.B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)O1.C([O-])(=O)C.[Na+]>CN(C=O)C.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C(Cl)Cl.Cl[Pd]Cl.[Fe]>[CH3:16][Si:15]([CH3:18])([CH3:17])[CH2:14][CH2:13][O:12][CH2:11][N:8]1[C:5]2=[N:6][CH:7]=[CH:2][CH:3]=[C:4]2[CH:10]=[CH:9]1

Participants

Conditions

Temperature: 95 °C

Procedure

A mixture of (5-bromo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrrolo[2,3-b]pyridine 5.0 g, 15.3 mmol), bis(pinacolato)diboron (7.8 g, 30.6 mmol), dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (559 mg, 0.8 mmol), and sodium acetate (3.8, 45.8 mmol) in DMF (20 ml) was stirred at 95° C. overnight. The mixture was allowed to cool down to room temperature and then extracted with ethyl acetate (3×). The combined organic layers were extracted with brine, dried with Na2SO4, decanted, and concentrated to dryness. Silica chromatography of the crude using a gradient of ethyl acetate and hexane afforded 5-(4,4,5,5)-tetramethyl[1,3,2]dioxa-borolan-2-yl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrrolo[2,3-b]pyridine (5.0 g, 88% yield). 1H NMR (500 MHz, DMSO-d6) δ 0.02 (s, 9H), 0.95 (, 2H), 1.45 (s, 2H), 3.65 (m, 2H), 5.75 (s, 2H), 6.70 (s, 1H), 7.75 (s, 1H), 8.40 (s, 1H), 8.60 (s, 1H). MS: m/z 375.2 (M+H+).

Workup

temperatureto cool down to room temperature
extractionextracted with ethyl acetate (3×)
extractionThe combined organic layers were extracted with brine
dry with materialdried with Na2SO4
customdecanted
concentrationconcentrated to dryness

Sources & evidence

ORD record: ord-37b942d93b47484dbd4a61c9f8f24cd5
Source dataset: uspto-grants-2012_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08242280B2

Reaction notes

Loading…