Enantioselective cyanation of benzylic c-h bonds via copper-catalyzed radical relay
文献类型：期刊论文
| 作者 | Zhang, Wen1; Wang, Fei1; McCann, Scott D.2; Wang, Dinghai1; Chen, Pinhong1; Stahl, Shannon S.2; Liu, Guosheng1 |
| 刊名 | Science
 |
| 出版日期 | 2016-09-02 |
| 卷号 | 353期号:6303页码:1014-1018 |
| ISSN号 | 0036-8075 |
| DOI | 10.1126/science.aaf7783 |
| 通讯作者 | Stahl, shannon s.(stahl@chem.wisc.edu) ; Liu, guosheng(gliu@mail.sioc.ac.cn) |
| 英文摘要 | Direct methods for stereoselective functionalization of sp(3)-hybridized carbon-hydrogen [c(sp(3))-h] bonds in complex organic molecules could facilitate much more efficient preparation of therapeutics and agrochemicals. here, we report a copper-catalyzed radical relay pathway for enantioselective conversion of benzylic c-h bonds into benzylic nitriles. hydrogen-atom abstraction affords an achiral benzylic radical that undergoes asymmetric c(sp(3))-cn bond formation upon reaction with a chiral copper catalyst. the reactions proceed efficiently at room temperature with the benzylic substrate as limiting reagent, exhibit broad substrate scope with high enantioselectivity (typically 90 to 99% enantiomeric excess), and afford products that are key precursors to important bioactive molecules. mechanistic studies provide evidence for diffusible organic radicals and highlight the difference between these reactions and c-h oxidations mediated by enzymes and other catalysts that operate via radical rebound pathways. |
| WOS关键词 | ALKYL ELECTROPHILES ; ALLYLIC OXIDATION ; C(SP(3))-H BONDS ; CROSS-COUPLINGS ; FUNCTIONALIZATION ; HYDROCYANATION ; ALKENES ; OLEFINS ; BUTYL ; PHOTOREDOX |
| WOS研究方向 | Science & Technology - Other Topics |
| WOS类目 | Multidisciplinary Sciences |
| 语种 | 英语 |
| WOS记录号 | WOS:000382558900035 |
| 出版者 | AMER ASSOC ADVANCEMENT SCIENCE |
| URI标识 | http://www.irgrid.ac.cn/handle/1471x/2375639 |
| 专题 | 中国科学院大学 |
| 通讯作者 | Stahl, Shannon S.; Liu, Guosheng |
| 作者单位 | 1.Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Chinese Acad Sci, State Key Lab Organometall Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China 2.Univ Wisconsin, Dept Chem, 1101 Univ Ave, Madison, WI 53706 USA |
| 推荐引用方式 GB/T 7714 | Zhang, Wen,Wang, Fei,McCann, Scott D.,et al. Enantioselective cyanation of benzylic c-h bonds via copper-catalyzed radical relay[J]. Science,2016,353(6303):1014-1018. |
| APA | Zhang, Wen.,Wang, Fei.,McCann, Scott D..,Wang, Dinghai.,Chen, Pinhong.,...&Liu, Guosheng.(2016).Enantioselective cyanation of benzylic c-h bonds via copper-catalyzed radical relay.Science,353(6303),1014-1018. |
| MLA | Zhang, Wen,et al."Enantioselective cyanation of benzylic c-h bonds via copper-catalyzed radical relay".Science 353.6303(2016):1014-1018. |
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来源：中国科学院大学
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