1) Intramolecular nitrile oxide cyclization (INOC). Part II

SyntheticPage 487
Published Feb 14, 2011

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Procedure

A solution of  POCl₃ (1.00 mmol, 0.093 mL) in CHCl₃ (3.5 mL) was added dropwise to a mixture of N-allyl-N-(2-(cyclohexylamino)-2-oxo-1-phenylethyl)-3-nitropropanamide (0.670 mmol, 250 mg) and Et₃N (2.68 mmol, 0.373 mL) in CHCl₃ (3.5 mL). After 30 min Et₃N (1.33 mmol, 0.186 mL) POCl₃ (0.499 mmol, 0.0465 mL) in CHCl₃ (1.5 mL) were added and the reaction mixture was stirred for 2 h at room temperature under nitrogen atmosphere at which point water (20 mL) was added. The crude product was extracted with CH₂Cl₂ (3 x 15 mL) and dried over anhydrous MgSO₄. After evaporation of the organic solvent, the crude product was purified by flash chromatography using silica gel (eluent: ethyl acetate-hexane; 1 : 1) to obtain title compound as a white solid (168 mg, 71% yield,  mp 192-194 ^°C, R_f= 0.20   (ethyl acetate-hexane; 1 : 1). 50:50 Mixture of diastereoisomers as determined by ¹H-NMR integration.

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2) Vilsmeier-Haack aroylation of 1-Benzoylmorpholine

SyntheticPage 651
Published Jul 24, 2013

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Procedure

1-Benzoylmorpholine (2.38 g, 12.5 mmol) and freshly distilled POCl₃ (2.5 mL, 26.8 mmol) were mixed under an atmosphere of dinitrogen. The suspension was heated to 35 ºC until the solids were dissolved. The reaction was stirred at ambient temperature for another 5 h before pyrrole (0.55 g, 8.2 mmol) in dry 1,2- dichloroethene (ca. 50 mL) was added quickly. This was stirred overnight. Saturated Na₂CO₃ was slowly added to the reaction solution until the aqueous layer reached pH ca. 8. The separated organic layer was collected and the aqueous solution further extracted to chloroform (4 x 25 mL). Organic solvents were combined and washed with brine (2 x 20 mL) and dried over Na2SO4. The solvents were removed under reduced pressure to leave an off-white product. (1.25 g, 89 %).

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