Hydrochloric Acid → HCID 66693394, compound

HRID 2367991Notes

Reaction equation

HRID 2367991 reaction equation
C([C:3]1[C:4]([B:22]2[O:26][C:25]([CH3:28])(C)C(C)(C)[O:23]2)=[C:5]([CH:19]=[CH:20][CH:21]=1)[O:6][CH2:7][CH2:8][CH2:9][CH2:10][NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=O.C[N+:32]([O-:34])=[O:33].[OH-].[Na+].Cl>CCCCCCCCCCCCCCCC[N+](C)(C)C.[Br-].C1COCC1.O>[C:14]([O:13][C:12](=[O:18])[NH:11][CH2:10][CH2:9][CH2:8][CH2:7][O:6][C:5]1[C:4]2[B:22]([OH:23])[O:26][CH:25]([CH2:28][N+:32]([O-:34])=[O:33])[C:3]=2[CH:21]=[CH:20][CH:19]=1)([CH3:15])([CH3:16])[CH3:17]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 6375NitromethaneHCID 14798Sodium HydroxideHCID 87111392HCID 87111392, compound

Product 1

HCID 66693394HCID 66693394, compoundYield 53.9%

Reagents, catalysts & solvents 3

HCID 5974Hexadecyltrimethylammonium BromideCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl 4-(3-formyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenoxy)-butylcarbamate (3.5 g, 8.3 mmol) and CTAB (cat.) in THF (50 mL) was added MeNO2(2.8 mL, 49 mmol), followed by an aqueous solution of NaOH (0.36 g, 9.1 mmol) in H2O (5 mL). The mixture was stirred at room temperature for 45 min. The cyclization was afforded by adding 2N HCl solution until pH=2 at 0° C. The reaction mixture was extracted with EtOAc (3×50 mL) and the organic layers were dried over anhydrous Na2SO4, and then concentrated in vacuo. The residue was purified by chromatography on silica gel (PE: EtOAc=3:1) to give the product as yellow oil (1.7 g, yield 53.6%). 1H NMR (400 MHz, DMSO-d6) δ 9.05 (s, 1H), 7.44-7.47 (t, 1H), 7.06-7.08 (d, 1H), 6.88-6.90 (d, 1H), 9.86 (t, 1H), 5.70-5.72 (m, 1H), 5.29-5.33 (m, 1H), 4.53-4.59 (m, 1H), 4.02-4.06 (t, 2H), 2.95-2.30 (m, 2H), 1.67-1.72 (m, 2H), 1.52-1.57 (m, 2H), 1.38 (s, 9H).

Workup

  1. customThe cyclization was afforded
  2. extractionThe reaction mixture was extracted with EtOAc (3×50 mL)
  3. dry with materialthe organic layers were dried over anhydrous Na2SO4
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by chromatography on silica gel (PE: EtOAc=3:1)

Sources & evidence

ORD record
ord-f7b7609880c541d89572246aa59b2ce6
Source dataset
uspto-grants-2014_04
Patent number
US08703742B2

Reaction notes

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