化学学报 ›› 2019, Vol. 77 ›› Issue (9): 922-926.DOI: 10.6023/A19050158 上一篇 下一篇
所属专题: 有机自由基化学
研究论文
汤娜娜a†, 邵鑫a†, 王明扬a, 吴新鑫a, 朱晨ab*()
投稿日期:
2019-05-01
发布日期:
2019-06-04
通讯作者:
朱晨
E-mail:chzhu@suda.edu.cn
基金资助:
Tang, Nanaa†, Shao, Xina†, Wang, Mingyanga, Wu, Xinxina, Zhu, Chenab*()
Received:
2019-05-01
Published:
2019-06-04
Contact:
Zhu, Chen
E-mail:chzhu@suda.edu.cn
Supported by:
文章分享
利用自由基参与的远端炔基迁移策略实现了非活化烯烃的炔基化反应. 以磺酰氯为试剂, 在可见光促进下形成三氟甲基自由基或芳基(烷基)磺酰基自由基, 随后加成到非活化烯烃上, 生成烷基自由基中间体, 继而诱导远端炔烃的分子内迁移, 得到三氟甲基炔基化或磺酰基炔基化产物. 该方法具有条件温和、底物易得以及官能团兼容性广等优点.
汤娜娜, 邵鑫, 王明扬, 吴新鑫, 朱晨. 磺酰氯参与的基于远端炔基迁移的非活化烯烃炔基化反应[J]. 化学学报, 2019, 77(9): 922-926.
Tang, Nana, Shao, Xin, Wang, Mingyang, Wu, Xinxin, Zhu, Chen. Sulfonyl Chlorides Mediated Alkynylation of Non-activated Alkenes via Distal Alkynyl Group Migration[J]. Acta Chimica Sinica, 2019, 77(9): 922-926.
Entry | Photocatalyst (3 mol%) | Base (x equiv.) | Solvent | Yield/% |
---|---|---|---|---|
1 | Ir{[dF(CF3)ppy]2-(dtbbpy)}PF6 | Na2CO3 (1.0) | CH3CN | <5 |
2 | Ir(ppy)2(dtbbpy)PF6 | Na2CO3 (1.0) | CH3CN | <5 |
3 | Ru(bpy)3Cl2?6H2O | Na2CO3 (1.0) | CH3CN | <5 |
4 | fac-Ir(ppy)3 | Na2CO3 (1.0) | CH3CN | 75 |
5 | fac-Ir(ppy)3 | Na2CO3 (0.8) | CH3CN | 57 |
6 | fac-Ir(ppy)3 | Na2CO3 (1.2) | CH3CN | 68 |
7 | fac-Ir(ppy)3 | Na2CO3 (1.0) | acetone | 68 |
8 | fac-Ir(ppy)3 | Na2CO3 (1.0) | DCM | 58 |
9 | fac-Ir(ppy)3 | Na2CO3 (1.0) | DMSO | <10 |
10 | fac-Ir(ppy)3 | Na2CO3 (1.0) | DMF | <10 |
Entry | Photocatalyst (3 mol%) | Base (x equiv.) | Solvent | Yield/% |
---|---|---|---|---|
1 | Ir{[dF(CF3)ppy]2-(dtbbpy)}PF6 | Na2CO3 (1.0) | CH3CN | <5 |
2 | Ir(ppy)2(dtbbpy)PF6 | Na2CO3 (1.0) | CH3CN | <5 |
3 | Ru(bpy)3Cl2?6H2O | Na2CO3 (1.0) | CH3CN | <5 |
4 | fac-Ir(ppy)3 | Na2CO3 (1.0) | CH3CN | 75 |
5 | fac-Ir(ppy)3 | Na2CO3 (0.8) | CH3CN | 57 |
6 | fac-Ir(ppy)3 | Na2CO3 (1.2) | CH3CN | 68 |
7 | fac-Ir(ppy)3 | Na2CO3 (1.0) | acetone | 68 |
8 | fac-Ir(ppy)3 | Na2CO3 (1.0) | DCM | 58 |
9 | fac-Ir(ppy)3 | Na2CO3 (1.0) | DMSO | <10 |
10 | fac-Ir(ppy)3 | Na2CO3 (1.0) | DMF | <10 |
Entry | CF3SO2Cl (x equiv.) | Photocatalyst (y mol%) | Base (z equiv.) | Solvent | Yield/% |
---|---|---|---|---|---|
1 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.8) | CH3CN | 29 |
2 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.8) | acetone | 50 |
3 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.8) | MeOH | 45 |
4 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.8) | DMA | 33 |
5 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.8) | DMSO | ND |
6 | 1.5 | fac-Ir(ppy)3 (3%) | Na2HPO4 (0.8) | acetone | 40 |
7 | 1.5 | fac-Ir(ppy)3 (3%) | Na2CO3 (0.8) | acetone | 36 |
8 | 1.5 | fac-Ir(ppy)3 (3%) | K2CO3 (0.8) | acetone | 42 |
9 | 1.5 | fac-Ir(ppy)3 (3%) | NaHCO3 (0.8) | acetone | 48 |
10 | 1.5 | fac-Ir(ppy)3 (3%) | DABCO (0.8) | acetone | 27 |
11 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.7) | acetone | 43 |
12 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.9) | acetone | 47 |
13 | 1.5 | fac-Ir(ppy)3 (4%) | K2HPO4 (0.8) | acetone | 52 |
14 | 2.2 | fac-Ir(ppy)3 (4%) | K2HPO4 (0.8) | acetone | 54 |
15b | 2.2 | fac-Ir(ppy)3 (4%) | K2HPO4 (0.8) | acetone | 64 |
16b | 2.2 | Ru(bpy)3Cl2?6H2O (4%) | K2HPO4 (0.8) | acetone | ND |
17b | 2.2 | Ir(ppy)2(dtbbpy)PF6 (4%) | K2HPO4 (0.8) | acetone | ND |
18b | 2.2 | none | K2HPO4 (0.8) | acetone | ND |
19b,c | 2.2 | fac-Ir(ppy)3 (4%) | K2HPO4 (0.8) | acetone | ND |
Entry | CF3SO2Cl (x equiv.) | Photocatalyst (y mol%) | Base (z equiv.) | Solvent | Yield/% |
---|---|---|---|---|---|
1 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.8) | CH3CN | 29 |
2 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.8) | acetone | 50 |
3 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.8) | MeOH | 45 |
4 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.8) | DMA | 33 |
5 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.8) | DMSO | ND |
6 | 1.5 | fac-Ir(ppy)3 (3%) | Na2HPO4 (0.8) | acetone | 40 |
7 | 1.5 | fac-Ir(ppy)3 (3%) | Na2CO3 (0.8) | acetone | 36 |
8 | 1.5 | fac-Ir(ppy)3 (3%) | K2CO3 (0.8) | acetone | 42 |
9 | 1.5 | fac-Ir(ppy)3 (3%) | NaHCO3 (0.8) | acetone | 48 |
10 | 1.5 | fac-Ir(ppy)3 (3%) | DABCO (0.8) | acetone | 27 |
11 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.7) | acetone | 43 |
12 | 1.5 | fac-Ir(ppy)3 (3%) | K2HPO4 (0.9) | acetone | 47 |
13 | 1.5 | fac-Ir(ppy)3 (4%) | K2HPO4 (0.8) | acetone | 52 |
14 | 2.2 | fac-Ir(ppy)3 (4%) | K2HPO4 (0.8) | acetone | 54 |
15b | 2.2 | fac-Ir(ppy)3 (4%) | K2HPO4 (0.8) | acetone | 64 |
16b | 2.2 | Ru(bpy)3Cl2?6H2O (4%) | K2HPO4 (0.8) | acetone | ND |
17b | 2.2 | Ir(ppy)2(dtbbpy)PF6 (4%) | K2HPO4 (0.8) | acetone | ND |
18b | 2.2 | none | K2HPO4 (0.8) | acetone | ND |
19b,c | 2.2 | fac-Ir(ppy)3 (4%) | K2HPO4 (0.8) | acetone | ND |
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