Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination
Given the periodic relationship of phosphines and arsines, is remodeling the catalytic asymmetric hydrophosphination reaction an efficient manner to develop the corresponding hydroarsination reaction? Herein, a chiral PCP-Pd(II) pincer complex adept at generating enantioenriched phosphines was exami...
| Main Authors: | , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2021
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| Online Access: | https://hdl.handle.net/10356/150654 |
| _version_ | 1824454588429762560 |
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| author | Tay, Wee Shan Yang, Xiang-Yuan Li, Yongxin Pullarkat, Sumod A. Leung, Pak-Hing |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Tay, Wee Shan Yang, Xiang-Yuan Li, Yongxin Pullarkat, Sumod A. Leung, Pak-Hing |
| author_sort | Tay, Wee Shan |
| collection | NTU |
| description | Given the periodic relationship of phosphines and arsines, is remodeling the catalytic asymmetric hydrophosphination reaction an efficient manner to develop the corresponding hydroarsination reaction? Herein, a chiral PCP-Pd(II) pincer complex adept at generating enantioenriched phosphines was examined in the asymmetric hydroarsination reaction. Under distinct conditions, tertiary phosphines and arsines were generated in excellent yields (P: 96%, As: 91%) and ees (P: 90%, As: 85%). While secondary arsine reagents were not direct substitutes for the analogous phosphines, important parameters were identified which increased yield and ee of the hydroarsination reaction. Unlike the PCP-PdOAc pincer complex commonly used for hydrophosphinations, hydroarsination reactions involved a PCP-PdCl catalyst with 10 equiv. of CsF for optimal performance. Notable differences between the two reactions and their workup procedures were highlighted to guide further developments in the field. Lastly, respective mechanisms were proposed and contrasted for the activation of HEPh₂ (E = P, As). |
| first_indexed | 2025-02-19T03:24:42Z |
| format | Journal Article |
| id | ntu-10356/150654 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2025-02-19T03:24:42Z |
| publishDate | 2021 |
| record_format | dspace |
| spelling | ntu-10356/1506542021-08-03T13:20:33Z Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination Tay, Wee Shan Yang, Xiang-Yuan Li, Yongxin Pullarkat, Sumod A. Leung, Pak-Hing School of Physical and Mathematical Sciences Science::Chemistry Cross-coupling Reactions Enantioselective Hydrophosphination Given the periodic relationship of phosphines and arsines, is remodeling the catalytic asymmetric hydrophosphination reaction an efficient manner to develop the corresponding hydroarsination reaction? Herein, a chiral PCP-Pd(II) pincer complex adept at generating enantioenriched phosphines was examined in the asymmetric hydroarsination reaction. Under distinct conditions, tertiary phosphines and arsines were generated in excellent yields (P: 96%, As: 91%) and ees (P: 90%, As: 85%). While secondary arsine reagents were not direct substitutes for the analogous phosphines, important parameters were identified which increased yield and ee of the hydroarsination reaction. Unlike the PCP-PdOAc pincer complex commonly used for hydrophosphinations, hydroarsination reactions involved a PCP-PdCl catalyst with 10 equiv. of CsF for optimal performance. Notable differences between the two reactions and their workup procedures were highlighted to guide further developments in the field. Lastly, respective mechanisms were proposed and contrasted for the activation of HEPh₂ (E = P, As). Ministry of Education (MOE) Nanyang Technological University W. S. T. acknowledges NTU for the award of a research scholarship. The MOE Tier 1 grant (M4011537 RG108/15) is acknowledged for funding this work. We are also grateful to Prof. S. B. Wild of the Australian National University for his insightful discussions which contributed to this work. 2021-08-03T13:20:32Z 2021-08-03T13:20:32Z 2019 Journal Article Tay, W. S., Yang, X., Li, Y., Pullarkat, S. A. & Leung, P. (2019). Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination. Dalton Transactions, 48(14), 4602-4610. https://dx.doi.org/10.1039/C9DT00221A 1477-9226 https://hdl.handle.net/10356/150654 10.1039/C9DT00221A 14 48 4602 4610 en M4011537 RG108/15 Dalton Transactions © 2019 The Royal Society of Chemistry. All rights reserved. |
| spellingShingle | Science::Chemistry Cross-coupling Reactions Enantioselective Hydrophosphination Tay, Wee Shan Yang, Xiang-Yuan Li, Yongxin Pullarkat, Sumod A. Leung, Pak-Hing Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination |
| title | Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination |
| title_full | Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination |
| title_fullStr | Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination |
| title_full_unstemmed | Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination |
| title_short | Investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination |
| title_sort | investigating palladium pincer complexes in catalytic asymmetric hydrophosphination and hydroarsination |
| topic | Science::Chemistry Cross-coupling Reactions Enantioselective Hydrophosphination |
| url | https://hdl.handle.net/10356/150654 |
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