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4,4,5,5-Tetramethyl[1,3,2]dioxaborolane → 5-methoxy-1-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole

HRID 1628016
Notes
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Reaction equation

HRID 1628016 reaction equation
I[C:2]1[C:10]2[C:5](=[CH:6][CH:7]=[C:8]([O:11][CH3:12])[CH:9]=2)[N:4]([CH3:13])[CH:3]=1.[CH3:14][C:15]1([CH3:22])[C:19]([CH3:21])([CH3:20])[O:18][BH:17][O:16]1>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].C(Cl)Cl>[CH3:12][O:11][C:8]1[CH:9]=[C:10]2[C:5](=[CH:6][CH:7]=1)[N:4]([CH3:13])[CH:3]=[C:2]2[B:17]1[O:18][C:19]([CH3:21])([CH3:20])[C:15]([CH3:22])([CH3:14])[O:16]1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 2

HCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 534021023-Iodo-5-methoxy-1-methyl-1H-indole

Product 1

HCID 580098415-methoxy-1-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indoleYield 37.3%

Reagents, catalysts & solvents 2

HCID 178418807HCID 178418807, compoundCatalyst
HCID 31275
1,4-Dioxane
Solvent

Conditions

Temperature
100 °C

Procedure

The 3-iodo-5-methoxy-1-methyl-1H-indole (9.90 g, 34.5 mmol) in 1,4-dioxane (200 mL) was treated with PdCl2(dppf)-CH2Cl2 (1.41 g, 1.72 mmol), TEA (33.6 mL, 241 mmol) and 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (28.7 g, 224 mmol). The mixture was heated to about 100° C. for about 40 min. The mixture was cooled to rt and concentrated under reduced pressure. The material was stirred with EtOAc (300 mL) at rt for about 30 min and then filtered. The filtrate was concentrated under reduced pressure and the residue was purified by silica gel chromatography eluting with 100% DCM to give 5-methoxy-1-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (3.7 g, 37%): LC/MS (Table 2, Method a) Rt=2.68 min; MS m/z 288 (M+H)+.

Workup

  1. temperatureThe mixture was cooled to rt
  2. concentrationconcentrated under reduced pressure
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated under reduced pressure
  5. customthe residue was purified by silica gel chromatography
  6. washeluting with 100% DCM

Sources & evidence

ORD record
ord-94d65d28218b4939b3c2a52395f322dd
Source dataset
uspto-grants-2014_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08785639B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes