Potassium Carbonate → Formate

HRID 1399886Notes

Reaction equation

HRID 1399886 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[N:9]=[CH:8][N:7]([CH:10]3[CH2:13][N:12]([CH3:14])[CH2:11]3)[C:6]=2[CH:15]=1.[CH2:16]1[C:25]2[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=2)[CH2:19][CH2:18][N:17]1[CH2:26][CH:27]([OH:45])[CH2:28][O:29][C:30]1[CH:35]=[CH:34][CH:33]=[C:32](B2OC(C)(C)C(C)(C)O2)[CH:31]=1.[C:46]([O-])([O-:48])=[O:47].[K+].[K+]>O.O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:16]1[C:25]2[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=2)[CH2:19][CH2:18][N:17]1[CH2:26][CH:27]([OH:45])[CH2:28][O:29][C:30]1[CH:35]=[CH:34][CH:33]=[C:32]([C:2]2[CH:3]=[CH:4][C:5]3[N:9]=[CH:8][N:7]([CH:10]4[CH2:13][N:12]([CH3:14])[CH2:11]4)[C:6]=3[CH:15]=2)[CH:31]=1.[CH:46]([O-:48])=[O:47]

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 867292361-(3,4-dihydroisoquinolin-2(1H)-yl)-3-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenoxy)propan-2-olHCID 86729282HCID 86729282, compound

Product 2

HCID 283FormateYield 81.7%HCID 86729283HCID 86729283, compound

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
100 °C

Procedure

A mixture of 6-bromo-1-(1-methylazetidin-3-yl)-1H-benzo[d]imidazole (105 mg, 0.389 mmol), 1-(3,4-dihydroisoquinolin-2(1H)-yl)-3-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenoxy)propan-2-ol (162 mg, 0.389 mmol), Pd(dppf)Cl2 (30 mg, 0.039 mmol) and K2CO3 (265 mg, 1.17 mmol) in H2O-dioxane (1.5 mL/4.5 mL) was stirred at 100° C. under microwave heating for 15 min. The solvent was then removed by concentration and the residue purified by prep-HPLC to afford the title compound as a formate salt (14.3 mg, yield: 7.7%). 1H NMR (400 MHz, MeOD): δ 8.57 (s, 1H), 8.43 (s, 1H), 7.84-7.77 (m, 2H), 7.62-7.60 (m, 1H), 7.44-7.40 (m, 1H), 7.35-7.25 (m, 5H), 7.21 (d, J=7.2 Hz, 1H), 7.00 (dd, J=8, 1.6 Hz, 1H), 5.53-5.49 (m, 1H), 4.53 (dd, J=9.2, 4 Hz, 1H), 4.46 (s, 2H), 4.40-4.36 (m, 2H), 4.25-4.16 (m, 4H), 3.60 (t, J=6.4 Hz, 2H), 3.47-3.43 (m, 2H), 3.33-3.21 (m, 2H), 2.81 (s, 3H) ppm; ESI-MS (m/z): 469.3 [M+1]+.

Workup

  1. temperatureheating for 15 min
  2. customThe solvent was then removed by concentration
  3. customthe residue purified by prep-HPLC

Sources & evidence

ORD record
ord-3992357d33134af8983e62f8a796364a
Source dataset
uspto-grants-2014_12
Patent number
US08906900B2

Reaction notes

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