Pinacol → HCID 57537467, compound

HRID 1693729Notes

Reaction equation

HRID 1693729 reaction equation
C([Mg]Cl)(C)C.[Li]Cl.Br[C:9]1[C:10]([Cl:33])=[C:11]2[C:17]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[F:24])=[CH:16][N:15]([CH2:25][O:26][CH2:27][CH2:28][Si:29]([CH3:32])([CH3:31])[CH3:30])[C:12]2=[N:13][CH:14]=1.[B:34]([O:43][CH:44]([CH3:46])[CH3:45])([O:39][CH:40]([CH3:42])[CH3:41])OC(C)C.OC(C(O)(C)C)(C)C>C1COCC1>[Cl:33][C:10]1[C:9]([B:34]2[O:39][C:40]([CH3:41])([CH3:42])[C:44]([CH3:45])([CH3:46])[O:43]2)=[CH:14][N:13]=[C:12]2[N:15]([CH2:25][O:26][CH2:27][CH2:28][Si:29]([CH3:32])([CH3:31])[CH3:30])[CH:16]=[C:17]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=3[F:24])[C:11]=12

Participants

6

Reactant 4

HCID 6425PinacolHCID 21531Triisopropyl borateHCID 57537459HCID 57537459, compoundHCID 178461734HCID 178461734, compound

Product 1

HCID 57537467HCID 57537467, compoundYield 63%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Isopropyl magnesium chloride/Li—Cl complex (10.7 ml, 10.9 mmol-14% in THF) was added dropwise to a solution of 5-bromo-4-chloro-3-(2-fluoro-phenyl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrrolo-[2,3-b]pyridine (2.5 g, 5.4 mmol) under nitrogen in THF at −20° C. The reaction was let to proceed at −20° C. for another 2 hours. Then triisopropyl borate (3.1 ml, 13.6 mmol) in THF was added dropwise and the reaction was continued at −20° C. for another hour. At this time pinacol (1.3 g, 10.9 mmol) was added. The reaction was stirred at room temperature overnight. The solvent was removed under vacuum. Silica chromatography of the crude using a gradient of ethyl acetate and hexane afforded 4-chloro-3-(2-fluoro-phenyl)-5-(4,4,5,5-tetramethyl[1,3,2]-dioxaborolan-2-yl)-1-(2-trimethylsilanyl-ethoxymethyl)-1H-pyrrolo[2,3-b]pyridine (1.0 g, 63% yield). 1H NMR (500 MHz, DMSO-d6) δ 0.01 (s, 9H), 0.94 (t, 2H), 1.58 (s, 12H), 3.69 (t, 2H), 5.81 (s, 2H), 7.40 (m, 2H), 7.56 (m, 2H), 7.99 (s, 1H), 8.40 (m, 1H). MS: m/z 503.2 (M+H+).

Workup

  1. waitthe reaction was continued at −20° C. for another hour
  2. customThe solvent was removed under vacuum

Sources & evidence

ORD record
ord-1f0940c9ba7e49a08eba69cc87884b61
Source dataset
uspto-grants-2012_04
Patent number
US08158647B2

Reaction notes

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