Lithium Hydroxide → HCID 136098510, compound

HRID 1507382Notes

Reaction equation

HRID 1507382 reaction equation
Cl[C:2]1[C:11]([C:12]([F:15])([F:14])[F:13])=[N:10][C:9]2[C:4](=[CH:5][CH:6]=[C:7]([OH:16])[CH:8]=2)[N:3]=1.C([O-])([O-])=O.[K+].[K+].CC1(C)C(C)(C)OB([C:31]2[CH2:36][CH2:35][CH:34]([C:37]([O:39]CC)=[O:38])[CH2:33][CH:32]=2)O1.[Li+].[OH-]>O1CCOCC1.O.CO.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]>[OH:16][C:7]1[CH:8]=[C:9]2[C:4](=[CH:5][CH:6]=1)[N:3]=[C:2]([C:31]1[CH2:36][CH2:35][CH:34]([C:37]([OH:39])=[O:38])[CH2:33][CH:32]=1)[C:11]([C:12]([F:15])([F:14])[F:13])=[N:10]2

Participants

9

Reactant 4

HCID 3939Lithium HydroxideHCID 11430Potassium CarbonateHCID 592787964-(4,4,5,5-Tetramethyl-(1,3,2)dioxaborolan-2-yl)cyclohex-3-ene-1-carboxylic acid ethyl esterHCID 136378631HCID 136378631, compound2×

Product 1

HCID 136098510HCID 136098510, compoundYield 88.5%

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 887MethanolSolventHCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

2-Chloro-3-(trifluoromethyl)quinoxalin-6-ol (Intermediate 14, 109 mg) was suspended with K2CO3 (97 mg), ethyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohex-3-enecarboxylate (117 mg), PdCl2(dppf) (13 mg) in dioxane (1 mL) and water (0.2 mL) in a sealed microwave tube and heated at 100° C. over 40 min with microwave. The resultant mixture was diluted with water (5 mL) and MeOH (2 mL) and treated with LiOH (65 mg) overnight. After filtration through a pad of Celite, the clear aqueous layer was acidified with 1N HCl to pH 3. After the suspended solution was stirred over 1 h, filtration and rinsing with water afforded the desired product (125 mg). 1H NMR (DMSO-d6 300 MHz): δ 12.30 (1H, s), 10.93 (1H, s), 8.04 (1H, d, J=9 Hz), 7.59 (1H, dd, J=3, 9 hz), 7.35 (1H, d, J=3 Hz), 5.84 (1H, s), 2.58 (1H, m), 2.34 (4H, m), 2.07 (1H, m), 1.75 (1H, m) ppm. MS (ESI): m/z 339.0 [M+1]+.

Workup

  1. filtrationAfter filtration through a pad of Celite
  2. filtrationfiltration
  3. washrinsing with water

Sources & evidence

ORD record
ord-8fabfdfa626c4249a5bc59ccb6d42461
Source dataset
uspto-grants-2015_12
Patent number
US09221810B2

Reaction notes

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