化学学报 ›› 2019, Vol. 77 ›› Issue (9): 927-931.DOI: 10.6023/A19040151 上一篇 下一篇
所属专题: 有机自由基化学
研究论文
投稿日期:
2019-04-30
发布日期:
2019-06-21
通讯作者:
屠树江,姜波
E-mail:laotu@jsnu.edu.cn;jiangchem@jsnu.edu.cn
基金资助:
Zhao, Qi, Tu, Shu-Jiang*(), Jiang, Bo*()
Received:
2019-04-30
Published:
2019-06-21
Contact:
Tu, Shu-Jiang,Jiang, Bo
E-mail:laotu@jsnu.edu.cn;jiangchem@jsnu.edu.cn
Supported by:
文章分享
报道了一类新颖的Fe(III)介导的形式上的非活性烯烃的氢炔化反应. 该反应利用Fe(acac)3与苯硅烷反应能原位产生氢自由基的特性实现了氢自由基诱导的1,4-烯炔的分子内1,2-炔基迁移, 合成了一系列α-炔酮类化合物, 产率中等到良好. 基于实验结果及文献报道, 提出了可能的反应机理, 其涉及氢自由基加成、3-exo-dig环化(反鲍德温规则)和 C—C键的断裂重组等. 此外, 该反应具有良好的官能团兼容性, 如雌酮衍生的1,4-烯炔也能成功参与该反应.
赵琦, 屠树江, 姜波. 氢自由基引发的1,2-炔基迁移[J]. 化学学报, 2019, 77(9): 927-931.
Zhao, Qi, Tu, Shu-Jiang, Jiang, Bo. Hydrogen Radical Initiated 1,2-Alkynyl Migration[J]. Acta Chimica Sinica, 2019, 77(9): 927-931.
Entry | Ratio (1a∶2a) | Base | Metal salt (x/equiv.) | Temp./℃ | Yieldb/% |
---|---|---|---|---|---|
1 | 1∶2 | — | Fe(acac)3 (0.5) | 80 | 11 |
2 | 1∶2 | NaHCO3 | Fe(acac)3 (0.5) | 80 | 34 |
3 | 1∶2 | NaHCO3 | Fe(acac)3 (0.1) | 80 | 12 |
4 | 1∶2 | NaHCO3 | Fe(acac)3 (1.0) | 80 | 41 |
5 | 1∶2 | Na2CO3 | Fe(acac)3 (1.0) | 80 | 32 |
6 | 1∶2 | NaHCO3 | Fe(acac)3 (1.0) | 100 | 56 |
7 | 1∶1.5 | NaHCO3 | Fe(acac)3 (1.0) | 100 | 52 |
8 | 1∶2 | NaHCO3 | Co(acac)3 (1.0) | 100 | Trace |
9 | 1∶2 | NaHCO3 | Fe(acac)3 (0.8) | 100 | 55 |
10 | 1∶2 | NaHCO3 | Fe(acac)3 (1.2) | 100 | 64 |
11 | 1∶2 | NaHCO3 | Fe(acac)3 (2.0) | 100 | 45 |
12c | 1∶2 | NaHCO3 | Fe(acac)3 (1.2) | 100 | 43 |
Entry | Ratio (1a∶2a) | Base | Metal salt (x/equiv.) | Temp./℃ | Yieldb/% |
---|---|---|---|---|---|
1 | 1∶2 | — | Fe(acac)3 (0.5) | 80 | 11 |
2 | 1∶2 | NaHCO3 | Fe(acac)3 (0.5) | 80 | 34 |
3 | 1∶2 | NaHCO3 | Fe(acac)3 (0.1) | 80 | 12 |
4 | 1∶2 | NaHCO3 | Fe(acac)3 (1.0) | 80 | 41 |
5 | 1∶2 | Na2CO3 | Fe(acac)3 (1.0) | 80 | 32 |
6 | 1∶2 | NaHCO3 | Fe(acac)3 (1.0) | 100 | 56 |
7 | 1∶1.5 | NaHCO3 | Fe(acac)3 (1.0) | 100 | 52 |
8 | 1∶2 | NaHCO3 | Co(acac)3 (1.0) | 100 | Trace |
9 | 1∶2 | NaHCO3 | Fe(acac)3 (0.8) | 100 | 55 |
10 | 1∶2 | NaHCO3 | Fe(acac)3 (1.2) | 100 | 64 |
11 | 1∶2 | NaHCO3 | Fe(acac)3 (2.0) | 100 | 45 |
12c | 1∶2 | NaHCO3 | Fe(acac)3 (1.2) | 100 | 43 |
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