Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system
We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(III) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpen...
| Main Authors: | , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2017
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| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/86888 http://hdl.handle.net/10220/44207 |
| _version_ | 1811677495636787200 |
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| author | Huang, Xiaoqiang Luo, Shipeng Burghaus, Olaf Webster, Richard David Harms, Klaus Meggers, Eric |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Huang, Xiaoqiang Luo, Shipeng Burghaus, Olaf Webster, Richard David Harms, Klaus Meggers, Eric |
| author_sort | Huang, Xiaoqiang |
| collection | NTU |
| description | We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(III) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpensive and readily available Hantzsch esters as the photoredox mediator, Rh-coordinated prochiral radicals generated by a selective photoinduced single electron reduction are trapped by allyl sulfones in a highly stereocontrolled fashion, providing radical allylation products with up to 97% ee. The hereby formed fragmented sulfonyl radicals are utilized via an enantioselective radical addition to form chiral sulfones, which minimizes waste generation. |
| first_indexed | 2024-10-01T02:38:17Z |
| format | Journal Article |
| id | ntu-10356/86888 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:38:17Z |
| publishDate | 2017 |
| record_format | dspace |
| spelling | ntu-10356/868882023-02-28T19:23:41Z Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system Huang, Xiaoqiang Luo, Shipeng Burghaus, Olaf Webster, Richard David Harms, Klaus Meggers, Eric School of Physical and Mathematical Sciences By-product Utilization Enantioselective Radicals We report an unusual reaction design in which a chiral bis-cyclometalated rhodium(III) complex enables the stereocontrolled chemistry of photo-generated carbon-centered radicals and at the same time catalyzes an enantioselective sulfonyl radical addition to an alkene. Specifically, employing inexpensive and readily available Hantzsch esters as the photoredox mediator, Rh-coordinated prochiral radicals generated by a selective photoinduced single electron reduction are trapped by allyl sulfones in a highly stereocontrolled fashion, providing radical allylation products with up to 97% ee. The hereby formed fragmented sulfonyl radicals are utilized via an enantioselective radical addition to form chiral sulfones, which minimizes waste generation. Published version 2017-12-28T04:25:36Z 2019-12-06T16:30:59Z 2017-12-28T04:25:36Z 2019-12-06T16:30:59Z 2017 Journal Article Huang, X., Luo, S., Burghaus, O., Webster, R. D., Harms, K., & Meggers, E. (2017). Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system. Chemical Science, 8(10), 7126-7131. 2041-6520 https://hdl.handle.net/10356/86888 http://hdl.handle.net/10220/44207 10.1039/C7SC02621H en Chemical Science © 2017 The Author(s) (published by Royal Society of Chemistry). This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. 6 p. application/pdf |
| spellingShingle | By-product Utilization Enantioselective Radicals Huang, Xiaoqiang Luo, Shipeng Burghaus, Olaf Webster, Richard David Harms, Klaus Meggers, Eric Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system |
| title | Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system |
| title_full | Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system |
| title_fullStr | Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system |
| title_full_unstemmed | Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system |
| title_short | Combining the catalytic enantioselective reaction of visible-light-generated radicals with a by-product utilization system |
| title_sort | combining the catalytic enantioselective reaction of visible light generated radicals with a by product utilization system |
| topic | By-product Utilization Enantioselective Radicals |
| url | https://hdl.handle.net/10356/86888 http://hdl.handle.net/10220/44207 |
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