Cobalt-catalyzed directed alkylation of arenes with primary and secondary alkyl halides
A cobalt–N-heterocyclic carbene catalyst allows ortho-alkylation of aromatic imines with unactivated primary and secondary alkyl chlorides and bromides under room-temperature conditions. The scope of the reaction encompasses or complements that of cobalt-catalyzed ortho-alkylation reactions with ole...
| Main Authors: | , |
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| Format: | Journal Article |
| Language: | English |
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2014
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| Online Access: | https://hdl.handle.net/10356/105074 http://hdl.handle.net/10220/20375 |
| _version_ | 1811677763498672128 |
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| author | Yoshikai, Naohiko Gao, Ke |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Yoshikai, Naohiko Gao, Ke |
| author_sort | Yoshikai, Naohiko |
| collection | NTU |
| description | A cobalt–N-heterocyclic carbene catalyst allows ortho-alkylation of aromatic imines with unactivated primary and secondary alkyl chlorides and bromides under room-temperature conditions. The scope of the reaction encompasses or complements that of cobalt-catalyzed ortho-alkylation reactions with olefins as alkylating agents that we developed previously. Stereochemical outcomes of secondary alkylation reactions suggest that the reaction involves single-electron transfer from a cobalt species to the alkyl halide to generate the corresponding alkyl radical. A cycloalkylated product obtained by this method can be transformed into unique spirocycles through manipulation of the directing group and the cycloalkyl groups. |
| first_indexed | 2024-10-01T02:42:32Z |
| format | Journal Article |
| id | ntu-10356/105074 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:42:32Z |
| publishDate | 2014 |
| record_format | dspace |
| spelling | ntu-10356/1050742023-02-28T19:45:29Z Cobalt-catalyzed directed alkylation of arenes with primary and secondary alkyl halides Yoshikai, Naohiko Gao, Ke School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Organic chemistry A cobalt–N-heterocyclic carbene catalyst allows ortho-alkylation of aromatic imines with unactivated primary and secondary alkyl chlorides and bromides under room-temperature conditions. The scope of the reaction encompasses or complements that of cobalt-catalyzed ortho-alkylation reactions with olefins as alkylating agents that we developed previously. Stereochemical outcomes of secondary alkylation reactions suggest that the reaction involves single-electron transfer from a cobalt species to the alkyl halide to generate the corresponding alkyl radical. A cycloalkylated product obtained by this method can be transformed into unique spirocycles through manipulation of the directing group and the cycloalkyl groups. Published version 2014-08-21T07:04:02Z 2019-12-06T21:45:41Z 2014-08-21T07:04:02Z 2019-12-06T21:45:41Z 2014 2014 Journal Article Yoshikai, N., & Gao, K. (2014). Cobalt-catalyzed directed alkylation of arenes with primary and secondary alkyl halides. Pure and Applied Chemistry, 86(3), 419–424. 0033-4545 https://hdl.handle.net/10356/105074 http://hdl.handle.net/10220/20375 10.1515/pac-2014-5005 en Pure and applied chemistry © 2014 IUPAC & De Gruyter. This paper was published in Pure and Applied Chemistry and is made available as an electronic reprint (preprint) with permission of IUPAC & De Gruyter. The paper can be found at the following official DOI: [http://dx.doi.org/10.1515/pac-2014-5005]. One print or electronic copy may be made for personal use only. Systematic or multiple reproduction, distribution to multiple locations via electronic or other means, duplication of any material in this paper for a fee or for commercial purposes, or modification of the content of the paper is prohibited and is subject to penalties under law. application/pdf |
| spellingShingle | DRNTU::Science::Chemistry::Organic chemistry Yoshikai, Naohiko Gao, Ke Cobalt-catalyzed directed alkylation of arenes with primary and secondary alkyl halides |
| title | Cobalt-catalyzed directed alkylation of arenes with primary and secondary alkyl halides |
| title_full | Cobalt-catalyzed directed alkylation of arenes with primary and secondary alkyl halides |
| title_fullStr | Cobalt-catalyzed directed alkylation of arenes with primary and secondary alkyl halides |
| title_full_unstemmed | Cobalt-catalyzed directed alkylation of arenes with primary and secondary alkyl halides |
| title_short | Cobalt-catalyzed directed alkylation of arenes with primary and secondary alkyl halides |
| title_sort | cobalt catalyzed directed alkylation of arenes with primary and secondary alkyl halides |
| topic | DRNTU::Science::Chemistry::Organic chemistry |
| url | https://hdl.handle.net/10356/105074 http://hdl.handle.net/10220/20375 |
| work_keys_str_mv | AT yoshikainaohiko cobaltcatalyzeddirectedalkylationofareneswithprimaryandsecondaryalkylhalides AT gaoke cobaltcatalyzeddirectedalkylationofareneswithprimaryandsecondaryalkylhalides |