Synthesis of phosphiranes via organoiron-catalyzed phosphinidene transfer to electron-deficient olefins
Herein is reported the structural characterization and scalable preparation of the elusive iron–phosphido complex FpP(t Bu)(F) (2-F, Fp = (Fe(h5 -C5H5)(CO)2)) and its precursor FpP(t Bu)(Cl) (2-Cl) in 51% and 71% yields, respectively. These phosphide complexes are proposed to be relevant to an...
| Main Authors: | , , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
Royal Society of Chemistry (RSC)
2023
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| Online Access: | https://hdl.handle.net/1721.1/148456 |
| _version_ | 1811073651574833152 |
|---|---|
| author | Xin, Tiansi Geeson, Michael B Zhu, Hui Qu, Zheng-Wang Grimme, Stefan Cummins, Christopher C |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Xin, Tiansi Geeson, Michael B Zhu, Hui Qu, Zheng-Wang Grimme, Stefan Cummins, Christopher C |
| author_sort | Xin, Tiansi |
| collection | MIT |
| description | Herein is reported the structural characterization and scalable preparation of the elusive iron–phosphido
complex FpP(t
Bu)(F) (2-F, Fp = (Fe(h5
-C5H5)(CO)2)) and its precursor FpP(t
Bu)(Cl) (2-Cl) in 51% and 71%
yields, respectively. These phosphide complexes are proposed to be relevant to an organoiron catalytic
cycle for phosphinidene transfer to electron-deficient alkenes. Examination of their properties led to the
discovery of a more efficient catalytic system involving the simple, commercially available organoiron
catalyst Fp2. This improved catalysis also enabled the preparation of new phosphiranes with high yields
(
t
BuPCH2CHR; R = CO2Me, 41%; R = CN, 83%; R = 4-biphenyl, 73%; R = SO2Ph, 71%; R = POPh2, 70%;
R = 4-pyridyl, 82%; R = 2-pyridyl, 67%; R = PPh3
+, 64%) and good diastereoselectivity, demonstrating
the feasibility of the phosphinidene group-transfer strategy in synthetic chemistry. Experimental and
theoretical studies suggest that the original catalysis involves 2-X as the nucleophile, while for the new
Fp2-catalyzed reaction they implicate a diiron–phosphido complex Fp2(Pt
Bu), 4, as the nucleophile
which attacks the electron-deficient olefin in the key first P–C bond-forming step. In both systems, the
initial nucleophilic attack may be accompanied by favorable five-membered ring formation involving
a carbonyl ligand, a (reversible) pathway competitive with formation of the three-membered ring found
in the phosphirane product. A novel radical mechanism is suggested for the new Fp2-catalyzed system. |
| first_indexed | 2024-09-23T09:36:25Z |
| format | Article |
| id | mit-1721.1/148456 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T09:36:25Z |
| publishDate | 2023 |
| publisher | Royal Society of Chemistry (RSC) |
| record_format | dspace |
| spelling | mit-1721.1/1484562023-03-10T03:44:18Z Synthesis of phosphiranes via organoiron-catalyzed phosphinidene transfer to electron-deficient olefins Xin, Tiansi Geeson, Michael B Zhu, Hui Qu, Zheng-Wang Grimme, Stefan Cummins, Christopher C Massachusetts Institute of Technology. Department of Chemistry Herein is reported the structural characterization and scalable preparation of the elusive iron–phosphido complex FpP(t Bu)(F) (2-F, Fp = (Fe(h5 -C5H5)(CO)2)) and its precursor FpP(t Bu)(Cl) (2-Cl) in 51% and 71% yields, respectively. These phosphide complexes are proposed to be relevant to an organoiron catalytic cycle for phosphinidene transfer to electron-deficient alkenes. Examination of their properties led to the discovery of a more efficient catalytic system involving the simple, commercially available organoiron catalyst Fp2. This improved catalysis also enabled the preparation of new phosphiranes with high yields ( t BuPCH2CHR; R = CO2Me, 41%; R = CN, 83%; R = 4-biphenyl, 73%; R = SO2Ph, 71%; R = POPh2, 70%; R = 4-pyridyl, 82%; R = 2-pyridyl, 67%; R = PPh3 +, 64%) and good diastereoselectivity, demonstrating the feasibility of the phosphinidene group-transfer strategy in synthetic chemistry. Experimental and theoretical studies suggest that the original catalysis involves 2-X as the nucleophile, while for the new Fp2-catalyzed reaction they implicate a diiron–phosphido complex Fp2(Pt Bu), 4, as the nucleophile which attacks the electron-deficient olefin in the key first P–C bond-forming step. In both systems, the initial nucleophilic attack may be accompanied by favorable five-membered ring formation involving a carbonyl ligand, a (reversible) pathway competitive with formation of the three-membered ring found in the phosphirane product. A novel radical mechanism is suggested for the new Fp2-catalyzed system. 2023-03-09T19:57:57Z 2023-03-09T19:57:57Z 2022 2023-03-09T19:55:15Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/148456 Xin, Tiansi, Geeson, Michael B, Zhu, Hui, Qu, Zheng-Wang, Grimme, Stefan et al. 2022. "Synthesis of phosphiranes via organoiron-catalyzed phosphinidene transfer to electron-deficient olefins." Chemical Science, 13 (43). en 10.1039/D2SC05011K Chemical Science Creative Commons Attribution 4.0 International license https://creativecommons.org/licenses/by/4.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry (RSC) |
| spellingShingle | Xin, Tiansi Geeson, Michael B Zhu, Hui Qu, Zheng-Wang Grimme, Stefan Cummins, Christopher C Synthesis of phosphiranes via organoiron-catalyzed phosphinidene transfer to electron-deficient olefins |
| title | Synthesis of phosphiranes via organoiron-catalyzed phosphinidene transfer to electron-deficient olefins |
| title_full | Synthesis of phosphiranes via organoiron-catalyzed phosphinidene transfer to electron-deficient olefins |
| title_fullStr | Synthesis of phosphiranes via organoiron-catalyzed phosphinidene transfer to electron-deficient olefins |
| title_full_unstemmed | Synthesis of phosphiranes via organoiron-catalyzed phosphinidene transfer to electron-deficient olefins |
| title_short | Synthesis of phosphiranes via organoiron-catalyzed phosphinidene transfer to electron-deficient olefins |
| title_sort | synthesis of phosphiranes via organoiron catalyzed phosphinidene transfer to electron deficient olefins |
| url | https://hdl.handle.net/1721.1/148456 |
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