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Kondrat’eva吡啶合成反應(yīng)

惡唑(氮雜二烯)和親二烯體通過(guò)反電子要求型雜-Diels–Alder反應(yīng),開(kāi)環(huán),芳構(gòu)化制備吡啶衍生物的反應(yīng)。此反應(yīng)由Kondrat’eva在1957年首次報(bào)道【Kondrat’eva, G. Ya., Khim. Nauk. Prom.19572, 666。
此反應(yīng)一個(gè)的應(yīng)用是合成Vitamin B6,  5-乙氧基-4-甲基惡唑和馬來(lái)酸酐進(jìn)行環(huán)加成,水解,還原得到產(chǎn)物。

Tetrahedron 1967,23, 943-955 】



反應(yīng)機(jī)理

機(jī)理和Boger吡啶合成反應(yīng)類似,惡唑(氮雜二烯)和親二烯體進(jìn)行反電子要求型的Hetero-Diels–Alder reaction(雜-Diels–Alder反應(yīng))得到雙環(huán)中間體,開(kāi)環(huán),消除芳構(gòu)化,得到吡啶類化合物。


反應(yīng)實(shí)例

A solution containing 0.1 g N-(4-methyloxazol-2-yl)-N-(pent-4-enyl)acetamide(0.5 mmol) and 0.06 g DBU (0.4 mmol) in 2 mL toluene in a sealed tube under an argonatmosphere was heated at 180?C for 20 h. Then the solvent was removed under reducedpressure, and the residue was purifified by flflash silica gel chromatography to give 0.3 g1-acetyl-7-methyl-1,2,3,4-tetrahydro-1,8-naphthyridine as a pale yellow oil, in a yield of39%. (Note: It requires 0.842 g starting material to afford 39% naphthyridine derivative ina yield of 39%, but it was stated as 0.1 g in the original article.)

J. Org. Chem.199964, 3595.




A solution of 0.15 g oxazole alcohol (0.41 mmol) and 0.05 g DBN (0.41 mmol) in 60 mLanhydrous o-dichlorobenzene was deoxygenated with argon for 45 min. The mixture washeated at 150?C under an argon atmosphere for 1.5 h and then cooled to room temperature.Upon removal of solvent in vacuo, the residue was purifified by flflash chromatography usingMeOH/EtOAc (1:49) as the eluent to afford 0.10 g pyridine alcohol as a pale yellow oil, ina yield of 71%.

J. Org. Chem.198954, 5580



J. Org. Chem. 1977, 42, 2039-2040 】


J. Org. Chem. 1984, 49, 4325-4332 】



Tetrahedron Lett.  2000,41,10251-10255 】



參考資料

Wang, Zerong (2010). Comprehensive Organic Name Reactions and Reagents || Kondrat'eva Pyridine Synthesis. 1668-1671.


相關(guān)反應(yīng)

Boger吡啶合成反應(yīng)

1,2,4-三嗪和親二烯體(如烯胺)通過(guò)雜原子D-A加成脫去N2得到吡啶的反應(yīng)。


雜-Diels–Alder反應(yīng)





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