(E)-Tert-Butyl 3-(Pyridin-2-Yl)Acrylate synthesis

7synthesis methods

Product Name:(E)-Tert-Butyl 3-(Pyridin-2-Yl)Acrylate
CAS Number:181517-75-9
Molecular formula:C12H15NO2
Molecular Weight:205.25

2-Propenoic acid, 3-(1-oxido-2-pyridinyl)-, 1,1-dimethylethyl ester, (2E)-

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181517-75-9
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Yield:181517-75-9 112 mg

Reaction Conditions:

with tetrahydroxydiboron in N,N-dimethyl-formamide;acetonitrile at 20; for 0.166667 h;

Steps:

Pyridine-N-oxide (326 mg, 3.43 mmol), pyridine (70.0 L, 0.86 mmol), Ag2CO3 (355 mg, 1.29 mmol) and Pd(OAc)2 (20 mg,0.09 mmol) were combined with tert-butylacrylate (110 mg, 0.86 mmol) in 1,4-dioxane (4 mL) and degassed with a steady stream of nitrogen for 10 minutes. The reaction was then sealed under nitrogen and heated to 120°C for 16hours. LCMS analysis indicated the initial coupling reaction was complete. The reaction was cooled and filtered through a plug of silica gel. The filtrate was concentrated and taken up in a 5:1 mixture of ACN:DMF. The solution was treated with tetrahydroxydiboron (511 mg, 5.70 mmol) in a single portion (NOTE: exotherm evident). After stirring at room temperature ten minutes, LCMS analysis indicated the reduction was complete. The reaction was quenched with water(10 mL), and the desired product extracted with ethyl acetate (3 x 10 mL), washed with brine, dried (Na2SO4) and evacuated. The crude material was triturated with water to afford the desired product. Compound 20 Entry 2 (112 mg, 64%, clear oil)1H NMR (400 MHz, CDCl3) 8.66 (d, J=4.3 Hz, 1H), 7.77 - 7.69 (m, 1H), 7.62 (d, J=16.0 Hz, 1H), 7.45 (d, J=7.8 Hz, 1H), 7.31- 7.27 (m, 1H), 7.29 - 7.25 (m, 2H), 6.86 (d, J=16.0 Hz, 1H), 1.56 (s, 9H). 13C NMR (100 MHz, CDCl3) 165.9, 153.2, 149.9,142.1, 136.8, 124.6, 123.9, 80.8, 28.2. m/z = 206.0 (M+H)+.

References:

Londregan, Allyn T.;Piotrowski, David W.;Xiao, Jun [Synlett,2013,vol. 24,# 20,art. no. ST-2013-S0695-L,p. 2695 - 2700] Location in patent:supporting information

109-04-6 Synthesis