Regioselective copper-catalyzed oxidative coupling of α-alkylated styrenes with tertiary alkyl radicals
A radical-mediated oxidative cross-coupling of readily accessible α-alkylated styrenes with 1,3-dicarbonyl compounds utilizing a combination of Cu(OAc)2 and air as a catalytic system is described. Rather than requiring α-halocarbonyl compounds, this efficient approach enables direct installation of...
| Main Authors: | , , , , |
|---|---|
| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2020
|
| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/138243 |
| _version_ | 1811694665152331776 |
|---|---|
| author | Wang, Cong Liu, Rui-Hua Tian, Ming-Qing Hu, Xu-Hong Loh, Teck-Peng |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Wang, Cong Liu, Rui-Hua Tian, Ming-Qing Hu, Xu-Hong Loh, Teck-Peng |
| author_sort | Wang, Cong |
| collection | NTU |
| description | A radical-mediated oxidative cross-coupling of readily accessible α-alkylated styrenes with 1,3-dicarbonyl compounds utilizing a combination of Cu(OAc)2 and air as a catalytic system is described. Rather than requiring α-halocarbonyl compounds, this efficient approach enables direct installation of tertiary functionalized alkyl motifs to olefins with simple carbonyl derivatives. The novel protocol is characterized with high allylic selectivities via a competing β-H elimination. Both radical-clock and -trapping experiments provided clear-cut evidence for the intermediacy of an α-keto carbon-centered radical. |
| first_indexed | 2024-10-01T07:11:11Z |
| format | Journal Article |
| id | ntu-10356/138243 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T07:11:11Z |
| publishDate | 2020 |
| record_format | dspace |
| spelling | ntu-10356/1382432020-04-29T08:24:10Z Regioselective copper-catalyzed oxidative coupling of α-alkylated styrenes with tertiary alkyl radicals Wang, Cong Liu, Rui-Hua Tian, Ming-Qing Hu, Xu-Hong Loh, Teck-Peng School of Physical and Mathematical Sciences Science::Chemistry Oxidative Coupling Radical A radical-mediated oxidative cross-coupling of readily accessible α-alkylated styrenes with 1,3-dicarbonyl compounds utilizing a combination of Cu(OAc)2 and air as a catalytic system is described. Rather than requiring α-halocarbonyl compounds, this efficient approach enables direct installation of tertiary functionalized alkyl motifs to olefins with simple carbonyl derivatives. The novel protocol is characterized with high allylic selectivities via a competing β-H elimination. Both radical-clock and -trapping experiments provided clear-cut evidence for the intermediacy of an α-keto carbon-centered radical. 2020-04-29T08:24:09Z 2020-04-29T08:24:09Z 2018 Journal Article Wang, C., Liu, R.-H., Tian, M.-Q., Hu, X.-H., & Loh, T.-P. (2018). Regioselective copper-catalyzed oxidative coupling of α-alkylated styrenes with tertiary alkyl radicals. Organic Letters, 20(13), 4032-4035. doi:10.1021/acs.orglett.8b01600 1523-7060 https://hdl.handle.net/10356/138243 10.1021/acs.orglett.8b01600 29943570 2-s2.0-85049626945 13 20 4032 4035 en Organic Letters © 2018 American Chemical Society. All rights reserved. |
| spellingShingle | Science::Chemistry Oxidative Coupling Radical Wang, Cong Liu, Rui-Hua Tian, Ming-Qing Hu, Xu-Hong Loh, Teck-Peng Regioselective copper-catalyzed oxidative coupling of α-alkylated styrenes with tertiary alkyl radicals |
| title | Regioselective copper-catalyzed oxidative coupling of α-alkylated styrenes with tertiary alkyl radicals |
| title_full | Regioselective copper-catalyzed oxidative coupling of α-alkylated styrenes with tertiary alkyl radicals |
| title_fullStr | Regioselective copper-catalyzed oxidative coupling of α-alkylated styrenes with tertiary alkyl radicals |
| title_full_unstemmed | Regioselective copper-catalyzed oxidative coupling of α-alkylated styrenes with tertiary alkyl radicals |
| title_short | Regioselective copper-catalyzed oxidative coupling of α-alkylated styrenes with tertiary alkyl radicals |
| title_sort | regioselective copper catalyzed oxidative coupling of α alkylated styrenes with tertiary alkyl radicals |
| topic | Science::Chemistry Oxidative Coupling Radical |
| url | https://hdl.handle.net/10356/138243 |
| work_keys_str_mv | AT wangcong regioselectivecoppercatalyzedoxidativecouplingofaalkylatedstyreneswithtertiaryalkylradicals AT liuruihua regioselectivecoppercatalyzedoxidativecouplingofaalkylatedstyreneswithtertiaryalkylradicals AT tianmingqing regioselectivecoppercatalyzedoxidativecouplingofaalkylatedstyreneswithtertiaryalkylradicals AT huxuhong regioselectivecoppercatalyzedoxidativecouplingofaalkylatedstyreneswithtertiaryalkylradicals AT lohteckpeng regioselectivecoppercatalyzedoxidativecouplingofaalkylatedstyreneswithtertiaryalkylradicals |