Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer
Acyl(chloro)phosphines RC(O)P(Cl)(t-Bu) have been prepared by formal insertion of tert-butyl phosphinidene (t-Bu-P) from t-BuPA (A = C14H10 or anthracene) into the C-Cl bond of acyl chlorides. We show that the under-explored acyl(chloro)phosphine functional group provides an efficient method to prep...
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| Format: | Article |
| Language: | English |
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Royal Society of Chemistry (RSC)
2020
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| Online Access: | https://hdl.handle.net/1721.1/125274 |
| _version_ | 1826193292169052160 |
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| author | Szkop, Kevin M. Geeson, Michael B. Stephan, Douglas W. Cummins, Christopher C |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Szkop, Kevin M. Geeson, Michael B. Stephan, Douglas W. Cummins, Christopher C |
| author_sort | Szkop, Kevin M. |
| collection | MIT |
| description | Acyl(chloro)phosphines RC(O)P(Cl)(t-Bu) have been prepared by formal insertion of tert-butyl phosphinidene (t-Bu-P) from t-BuPA (A = C14H10 or anthracene) into the C-Cl bond of acyl chlorides. We show that the under-explored acyl(chloro)phosphine functional group provides an efficient method to prepare bis(acyl)phosphines, which are important precursors to compounds used industrially as radical polymerization initiators. Experimental and computational investigations into the mechanism of formation of acyl(chloro)phosphines by our synthetic method reveal a pathway in which chloride attacks a phosphonium intermediate and leads to the reductive loss of anthracene from the phosphorus center in a P(v) to P(iii) process. The synthetic applicability of the acyl(chloro)phosphine functional group has been demonstrated by reduction to an acylphosphide anion, which can in turn be treated with an acyl chloride to furnish dissymmetric bis(acyl)phosphines. |
| first_indexed | 2024-09-23T09:36:41Z |
| format | Article |
| id | mit-1721.1/125274 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T09:36:41Z |
| publishDate | 2020 |
| publisher | Royal Society of Chemistry (RSC) |
| record_format | dspace |
| spelling | mit-1721.1/1252742022-09-30T15:41:10Z Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer Szkop, Kevin M. Geeson, Michael B. Stephan, Douglas W. Cummins, Christopher C Massachusetts Institute of Technology. Department of Chemistry Acyl(chloro)phosphines RC(O)P(Cl)(t-Bu) have been prepared by formal insertion of tert-butyl phosphinidene (t-Bu-P) from t-BuPA (A = C14H10 or anthracene) into the C-Cl bond of acyl chlorides. We show that the under-explored acyl(chloro)phosphine functional group provides an efficient method to prepare bis(acyl)phosphines, which are important precursors to compounds used industrially as radical polymerization initiators. Experimental and computational investigations into the mechanism of formation of acyl(chloro)phosphines by our synthetic method reveal a pathway in which chloride attacks a phosphonium intermediate and leads to the reductive loss of anthracene from the phosphorus center in a P(v) to P(iii) process. The synthetic applicability of the acyl(chloro)phosphine functional group has been demonstrated by reduction to an acylphosphide anion, which can in turn be treated with an acyl chloride to furnish dissymmetric bis(acyl)phosphines. National Science Foundation (CHE-1664799) 2020-05-15T20:11:17Z 2020-05-15T20:11:17Z 2019-02 2018-12 2019-12-13T19:38:31Z Article http://purl.org/eprint/type/JournalArticle 2041-6520 2041-6539 https://hdl.handle.net/1721.1/125274 Szkop, Kevin M. et al. "Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer." Chemical Science 10, 12 (February 2019): 3627-3631 © 2019 The Royal Society of Chemistry en http://dx.doi.org/10.1039/c8sc05657a Chemical Sicence Creative Commons Attribution 3.0 unported license https://creativecommons.org/licenses/by/3.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry (RSC) |
| spellingShingle | Szkop, Kevin M. Geeson, Michael B. Stephan, Douglas W. Cummins, Christopher C Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer |
| title | Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer |
| title_full | Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer |
| title_fullStr | Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer |
| title_full_unstemmed | Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer |
| title_short | Synthesis of acyl(chloro)phosphines enabled by phosphinidene transfer |
| title_sort | synthesis of acyl chloro phosphines enabled by phosphinidene transfer |
| url | https://hdl.handle.net/1721.1/125274 |
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