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25th September 2014 @ 06:20

Reaction performed in parallel to TM 60-1.

scheme

A 21 mL sample vial was oven dried, then allowed to cool under vacuum (using a teflon vial adapter fitted with a septum). A stirbar, 3 Å powdered molecular sieves (stored in an oven, then microwave activated; 150 mg), potassium carbonate (also stored in oven; 207 mg, 1.5 mmol), palladium acetate (5 mg, 2 mol %), and dcpp • 2HBF4 (25 mg, 4 mol %) were added to the vial, which was then evacuated for several minutes (avoiding disturbance of the finely powdered solid contents). Two nested balloons attached to a short section of tubing fitted with a stopcock were flushed three times with carbon monoxide, then filled (around 150 mL), and attached to a three-way valve connected to the vial and vacuum. The vial was evacuated and refilled with CO three time, then DMF (dried over 4 Å sieves, degassed by freeze-thawing, then stored over 4 Å sieves under argon; 1 mL), 3-chloropyridine (114 mg, 1 mmol, 0.95 uL), and ethanol (0.3 mL, ~5 mmol, 5 eq)) added by syringe.

The reaction mixture was heated to 110 °C for 5 hours, then diluted with EtOAc (~ 15 mL), filtered through a plug of celite, rinsed with more EtOAc (~25 mL), then concentrated on celite before purification by automatic column chromatography (silica, hexanes:EtOAc) to give one fraction.

Pure TM 61-1 was obtained as a white solid (80 mg, 53 %).

NMR:

1H (CDCl3, 500 MHz)

Ethyl picolinate 1H CDCl3 500 MHz.pdf

13C (CDCl3, 500 MHz)

Ethyl picolinate 13C CDCl3 500 MHz.pdf

carbonylative screening Ethyl pyridinyl.zip
Attached Files
scheme.png
HIRAC.pdf
Ethyl picolinate 1H CDCl3 500 MHz.pdf
Ethyl picolinate 13C CDCl3 500 MHz.pdf
carbonylative screening Ethyl pyridinyl.zip