Stereogenic lock in 1-naphthylethanamine complexes for catalyst and auxiliary design : structural and reactivity analysis for cycloiridated pseudotetrahedral complexes
A series of optically active pseudo-tetrahedral five-membered cyclometalated 1-naphthylethanamine iridium(III) complexes were prepared and characterized to analyze the efficacy of the stereogenic conformational lock in both solid and solution phases. The synthesis of the iridacycles was diastereosel...
| Main Authors: | , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2019
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| Online Access: | https://hdl.handle.net/10356/104477 http://hdl.handle.net/10220/49996 |
| _version_ | 1811677296351772672 |
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| author | Chen, Jeremy Houguang Teo, Ronald Hong Xiang Li, Yongxin Pullarkat, Sumod Appukuttan Leung, Pak-Hing |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Chen, Jeremy Houguang Teo, Ronald Hong Xiang Li, Yongxin Pullarkat, Sumod Appukuttan Leung, Pak-Hing |
| author_sort | Chen, Jeremy Houguang |
| collection | NTU |
| description | A series of optically active pseudo-tetrahedral five-membered cyclometalated 1-naphthylethanamine iridium(III) complexes were prepared and characterized to analyze the efficacy of the stereogenic conformational lock in both solid and solution phases. The synthesis of the iridacycles was diastereoselective, and the compounds were found to be conformationally rigid. In comparison to its phenyl derivative, the structural lock prevented oxidation of the amine moiety within the five-membered organometallic ring during its synthesis. With up to three stereogenic centers in one of the naphthalene complexes, the stereochemistry of the metallacycle remained stable to both thermal and chemical changes. In terms of catalytic performance, the complexes displayed excellent activity for the asymmetric hydrogen transfer reaction, albeit with modest enantioselectivities. |
| first_indexed | 2024-10-01T02:35:07Z |
| format | Journal Article |
| id | ntu-10356/104477 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:35:07Z |
| publishDate | 2019 |
| record_format | dspace |
| spelling | ntu-10356/1044772023-02-28T19:45:27Z Stereogenic lock in 1-naphthylethanamine complexes for catalyst and auxiliary design : structural and reactivity analysis for cycloiridated pseudotetrahedral complexes Chen, Jeremy Houguang Teo, Ronald Hong Xiang Li, Yongxin Pullarkat, Sumod Appukuttan Leung, Pak-Hing School of Physical and Mathematical Sciences Science::Chemistry::Biochemistry Stereogenic Cycloiridated Complex A series of optically active pseudo-tetrahedral five-membered cyclometalated 1-naphthylethanamine iridium(III) complexes were prepared and characterized to analyze the efficacy of the stereogenic conformational lock in both solid and solution phases. The synthesis of the iridacycles was diastereoselective, and the compounds were found to be conformationally rigid. In comparison to its phenyl derivative, the structural lock prevented oxidation of the amine moiety within the five-membered organometallic ring during its synthesis. With up to three stereogenic centers in one of the naphthalene complexes, the stereochemistry of the metallacycle remained stable to both thermal and chemical changes. In terms of catalytic performance, the complexes displayed excellent activity for the asymmetric hydrogen transfer reaction, albeit with modest enantioselectivities. MOE (Min. of Education, S’pore) Accepted version 2019-09-25T05:13:21Z 2019-12-06T21:33:40Z 2019-09-25T05:13:21Z 2019-12-06T21:33:40Z 2017 Journal Article Chen, J. H., Teo, R. H. X., Li, Y., Pullarkat, S. A., & Leung, P. H. (2017). Stereogenic lock in 1-naphthylethanamine complexes for catalyst and auxiliary design : structural and reactivity analysis for cycloiridated pseudotetrahedral complexes. Organometallics, 37(1), 99-106. doi:10.1021/acs.organomet.7b00760 0276-7333 https://hdl.handle.net/10356/104477 http://hdl.handle.net/10220/49996 10.1021/acs.organomet.7b00760 en Organometallics This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.organomet.7b00760 11 p. application/pdf |
| spellingShingle | Science::Chemistry::Biochemistry Stereogenic Cycloiridated Complex Chen, Jeremy Houguang Teo, Ronald Hong Xiang Li, Yongxin Pullarkat, Sumod Appukuttan Leung, Pak-Hing Stereogenic lock in 1-naphthylethanamine complexes for catalyst and auxiliary design : structural and reactivity analysis for cycloiridated pseudotetrahedral complexes |
| title | Stereogenic lock in 1-naphthylethanamine complexes for catalyst and auxiliary design : structural and reactivity analysis for cycloiridated pseudotetrahedral complexes |
| title_full | Stereogenic lock in 1-naphthylethanamine complexes for catalyst and auxiliary design : structural and reactivity analysis for cycloiridated pseudotetrahedral complexes |
| title_fullStr | Stereogenic lock in 1-naphthylethanamine complexes for catalyst and auxiliary design : structural and reactivity analysis for cycloiridated pseudotetrahedral complexes |
| title_full_unstemmed | Stereogenic lock in 1-naphthylethanamine complexes for catalyst and auxiliary design : structural and reactivity analysis for cycloiridated pseudotetrahedral complexes |
| title_short | Stereogenic lock in 1-naphthylethanamine complexes for catalyst and auxiliary design : structural and reactivity analysis for cycloiridated pseudotetrahedral complexes |
| title_sort | stereogenic lock in 1 naphthylethanamine complexes for catalyst and auxiliary design structural and reactivity analysis for cycloiridated pseudotetrahedral complexes |
| topic | Science::Chemistry::Biochemistry Stereogenic Cycloiridated Complex |
| url | https://hdl.handle.net/10356/104477 http://hdl.handle.net/10220/49996 |
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