Tandem Heck Reaction of Tertiary Enamides: A Novel Access to trans-2,5-Disubstituted-3-Pyrroline Derivatives
文献类型：期刊论文
| 作者 | He Ling1; Gu Mengdi2; Wang Dexian1; Zhao Liang2; Wang Meixiang2 |
| 刊名 | ACTA CHIMICA SINICA
 |
| 出版日期 | 2015-10-15 |
| 卷号 | 73期号:10页码:1018-1024 |
| 关键词 | tertiary enamide Heck reaction tandem reaction 3-pyrroline |
| 英文摘要 | 3-Pyrroline structure is a common scaffold in natural products and synthetic bioactive molecules. 3-Pyrroline derivatives are also important intermediates in organic synthesis. The synthetic study of 3-pyrroline compounds has therefore always attracted great attention. Tertiary enamides are a class of unique and versatile synthons. They are able to participate in intramolecular and intermolecular reactions with various electrophiles, affording diverse nitrogen-containing heterocyclic compounds. Recently, we attempted the Heck reaction of the five-membered cyclic tertiary enamides and discovered the formation of alpha-arylated product with the double bond being shifted. We then envisioned a tandem diarylation reaction to synthesize 2,5-disubstituted-3-pyrroline derivatives. Herein, we reported the investigation of the Heck reaction of cyclic tertiary enamides, a simple and convenient approach to trans-2,5-disubstituted-3-pyrrolines. Silver salts were found to be effective additives to accelerate the reaction, while PdCl2(PPh3)(2) appeared as the best catalyst to improve the regioselectivity. Under the optimized conditions, a variety of differently substituted aryl iodides reacted smoothly with N-benzoyl-2,3-dihydro-1H-pyrrole 2a to afford the desired products 4a similar to 4k in moderate to high yields. Other N-substituted enamide substrates 2b similar to 2e underwent similar tandem reactions to give the corresponding products in moderate chemical yields. A representative procedure for this reaction is as follows: to an oven-dried Schlenk tube was successively added PdCl2(PPh3)(2) (18 mg, 0.025 mmol, 5 mol%), AgNO3 (177 mg, 1.05 mmol, 2.1 equiv.), DABCO (168 mg, 1.5 mmol, 3.0 equiv.) and dry DMA (1.0 mL) under argon atmosphere. After stirring for 5 min at room temperature and the mixture turned black, aryl iodides 1a similar to 11(1.05 mmol) in DMA (1.0 mL) was introduced into the tube, following the addition of substrate 2a similar to 2f (0.50 mmol) in DMA (1.0 mL). The resulting mixture was stirred at 80 degrees C until starting enamides and mono-arylated compounds were consumed, which was monitored by TLC analysis. After filtration, extraction and concentration in vacuo, the reaction residue was flash chromatographed on a silica gel column eluted with a mixture of petroleum ether and ethyl acetate (V: V=6 :1) to give the pure product 4a similar to 4p. The resulting trans-2,5-diphenyl-3-pyrroline was converted to pyrrole and pyrrolidine derivative, respectively, by oxidation and reduction. |
| 收录类别 | SCI |
| 语种 | 英语 |
| 公开日期 | 2016-01-12 |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/29352]  |
| 专题 | 化学研究所_分子识别与功能实验室 |
| 作者单位 | 1.Chinese Acad Sci, CAS Key Lab Mol Recognit & Funct, Inst Chem, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China 2.Tsinghua Univ, MOE Key Lab Bioorgan Phosphorus Chem & Chem Biol, Beijing 100084, Peoples R China |
| 推荐引用方式 GB/T 7714 | He Ling,Gu Mengdi,Wang Dexian,et al. Tandem Heck Reaction of Tertiary Enamides: A Novel Access to trans-2,5-Disubstituted-3-Pyrroline Derivatives[J]. ACTA CHIMICA SINICA,2015,73(10):1018-1024. |
| APA | He Ling,Gu Mengdi,Wang Dexian,Zhao Liang,&Wang Meixiang.(2015).Tandem Heck Reaction of Tertiary Enamides: A Novel Access to trans-2,5-Disubstituted-3-Pyrroline Derivatives.ACTA CHIMICA SINICA,73(10),1018-1024. |
| MLA | He Ling,et al."Tandem Heck Reaction of Tertiary Enamides: A Novel Access to trans-2,5-Disubstituted-3-Pyrroline Derivatives".ACTA CHIMICA SINICA 73.10(2015):1018-1024. |
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来源：化学研究所
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