Diisopropylamine → 1-Adamantan-1-yl-3-pyridin-3-yl-propenone

HRID 234653Notes

Reaction equation

HRID 234653 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][C:14]([C:16]12[CH2:25][CH:20]3[CH2:21][CH:22]([CH2:24][CH:18]([CH2:19]3)[CH2:17]1)[CH2:23]2)=[O:15].[N:26]1[CH:31]=[CH:30][CH:29]=[C:28]([CH:32]=O)[CH:27]=1>C1COCC1.CCCCCC>[C:16]12([C:14](=[O:15])/[CH:13]=[CH:32]/[C:28]3[CH:27]=[N:26][CH:31]=[CH:30][CH:29]=3)[CH2:25][CH:20]3[CH2:21][CH:22]([CH2:24][CH:18]([CH2:19]3)[CH2:17]1)[CH2:23]2

Participants

7

Reactant 4

HCID 7912DiisopropylamineHCID 103713-PyridinecarboxaldehydeHCID 123126Methyl tricyclo(3.3.1.13,7)dec-1-yl ketone2×HCID 178418339Butyllithium

Product 1

HCID 57564281-Adamantan-1-yl-3-pyridin-3-yl-propenoneYield 70%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

To a stirred solution of diisopropylamine (1.54 ml, 11 mmol) in THF (40 ml) at 0° C. was added butyllithium (1.6M; 6.25 ml, 10.0 mmol) in hexane, followed after 5 minutes by 1-adamantyl methyl ketone (1.96 g, 11.0 mmol). After stirring for 30 minutes at 0° C. the resulting solution of the lithium enolate of 1-adamantyl methyl ketone was then added to a stirred solution of 3-pyridinecarboxaldehyde (0.94 ml, 10.0 mmol) in THF (12 ml) at room temperature. After 3 hours the mixture was partitioned between diethyl ether and water, and the ether layers were concentrated. Chromatography, on elution with petrol-ether-triethylamine, 100:50:1 afforded the product as a solid (1.87 g, 70%), which crystallised from hexane, m.p. 98°-101° C.; IR νmax 1679 cm-1 ; 1H-NMR (CDCl3) δ1.65-1.84 (12H, m, adamantyl CH2), 2.10 (3H, s, adamantyl CH), 7.27 (1H, d, J 15.8 Hz, COCHCH), 7.38 (1H, m, Py 5-H), 7.68 (1H, d, J 15.8 Hz, COCHCH), 7.93 (1H, m, Py 4-H), 8.55 (1H, m, Py 6-H), 8.81 (1H, m, Py 2-H); MS m/z 267 (M+).

Workup

  1. customAfter 3 hours the mixture was partitioned between diethyl ether and water
  2. concentrationthe ether layers were concentrated
  3. washChromatography, on elution with petrol-ether-triethylamine, 100:50:1

Sources & evidence

ORD record
ord-ccc7a27faa2a4415901516056704ccad
Source dataset
uspto-grants-1997_01
Patent number
US05595995

Reaction notes

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