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Dichloromethane → Ethyl 4-methyl-5-(2-oxaspiro[4.5]dec-7-en-8-yl)isoxazole-3-carboxylate

HRID 1478161
Notes
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Reaction equation

HRID 1478161 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH2:18][CH2:17][C:12]3([CH2:16][O:15][CH2:14][CH2:13]3)[CH2:11][CH:10]=2)O1.Br[C:21]1[O:25][N:24]=[C:23]([C:26]([O:28][CH2:29][CH3:30])=[O:27])[C:22]=1[CH3:31].C([O-])([O-])=O.[Cs+].[Cs+].C(Cl)Cl>COCCOC.O.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]>[CH3:31][C:22]1[C:23]([C:26]([O:28][CH2:29][CH3:30])=[O:27])=[N:24][O:25][C:21]=1[C:9]1[CH2:18][CH2:17][C:12]2([CH2:16][O:15][CH2:14][CH2:13]2)[CH2:11][CH:10]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 10796Cesium carbonateHCID 58828802Ethyl 5-bromo-4-methyl-1,2-oxazole-3-carboxylate2×HCID 1312893314,4,5,5-Tetramethyl-2-(2-oxaspiro[4.5]dec-7-en-8-yl)-1,3,2-dioxaborolane

Product 1

HCID 118511182Ethyl 4-methyl-5-(2-oxaspiro[4.5]dec-7-en-8-yl)isoxazole-3-carboxylate

Reagents, catalysts & solvents

3
HCID 44119782Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
90 °C

Procedure

[4,4,5,5-tetramethyl-2-(2-oxaspiro[4.5]dec-7-en-8-yl)-1,3,2-dioxaborolane] (0.172 g, 0.651 mmol), ethyl 5-bromo-4-methylisoxazole-3-carboxylate (Intermediate A) (0.183 g, 0.781 mmol) and Cs2CO3 (0.849 g, 2.60 mmol) were combined in DME (3 mL) and water (1.250 mL). PdCl2(dppf).CH2Cl2 adduct (0.016 g, 0.020 mmol) was added and the mixture was degassed thoroughly refilling with nitrogen. The mixture was stirred in the microwave at 90° C. for 1 hour. The biphasic reaction mixture was separated and the organic phase was adsorbed onto silica. Purification by chromatography eluting with a gradient of EtOAc in iso-hexane afforded the title compound;

Workup

  1. customthe mixture was degassed thoroughly
  2. customThe biphasic reaction mixture
  3. customwas separated
  4. customPurification by chromatography
  5. washeluting with a gradient of EtOAc in iso-hexane

Sources & evidence

ORD record
ord-8ce6b326991b49dabf6ad5e0c9a70a2f
Source dataset
uspto-grants-2016_08
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09403810B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes