Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes
Catalytic phosphiranation has been achieved, allowing preparation of trans-1-R-2-phenylphosphiranes (R = t-Bu: 1-t-Bu; i-Pr: 1-i-Pr) from the corresponding dibenzo-7-(R)-7-phospha-norbornadiene (RPA, A = C₁₄H₁₀, anthracene) and styrene in 73% and 57% isolated yields, respectively. The cocatalyst sys...
| Main Authors: | , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | English |
| Published: |
American Chemical Society (ACS)
2019
|
| Online Access: | https://hdl.handle.net/1721.1/122286 |
| _version_ | 1826215619765207040 |
|---|---|
| author | Geeson, Michael Baily Transue, Wesley Cummins, Christopher C |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Geeson, Michael Baily Transue, Wesley Cummins, Christopher C |
| author_sort | Geeson, Michael Baily |
| collection | MIT |
| description | Catalytic phosphiranation has been achieved, allowing preparation of trans-1-R-2-phenylphosphiranes (R = t-Bu: 1-t-Bu; i-Pr: 1-i-Pr) from the corresponding dibenzo-7-(R)-7-phospha-norbornadiene (RPA, A = C₁₄H₁₀, anthracene) and styrene in 73% and 57% isolated yields, respectively. The cocatalyst system requires tetramethylammonium fluoride (TMAF) and [Fp(THF)][BF₄] (Fp = Fe(η5-C₅H₅)(CO)₂). In the case of the t-Bu derivative, the reaction mechanism was probed using stoichiometric reaction studies, a Hammett analysis, and a deuterium labeling experiment. Together, these suggest the intermediacy of iron-phosphido FpP(F)(t-Bu) (2), generated independently from the stoichiometric reaction of [Fp(t-BuPA)][BF₄] with TMAF. Two other plausible reaction intermediates, [Fp(t-BuPA)][BF₄] and [Fp(1-t-Bu)][BF₄], were prepared independently and structurally characterized. |
| first_indexed | 2024-09-23T16:36:47Z |
| format | Article |
| id | mit-1721.1/122286 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T16:36:47Z |
| publishDate | 2019 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1222862022-10-02T08:27:30Z Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes Geeson, Michael Baily Transue, Wesley Cummins, Christopher C Massachusetts Institute of Technology. Department of Chemistry Catalytic phosphiranation has been achieved, allowing preparation of trans-1-R-2-phenylphosphiranes (R = t-Bu: 1-t-Bu; i-Pr: 1-i-Pr) from the corresponding dibenzo-7-(R)-7-phospha-norbornadiene (RPA, A = C₁₄H₁₀, anthracene) and styrene in 73% and 57% isolated yields, respectively. The cocatalyst system requires tetramethylammonium fluoride (TMAF) and [Fp(THF)][BF₄] (Fp = Fe(η5-C₅H₅)(CO)₂). In the case of the t-Bu derivative, the reaction mechanism was probed using stoichiometric reaction studies, a Hammett analysis, and a deuterium labeling experiment. Together, these suggest the intermediacy of iron-phosphido FpP(F)(t-Bu) (2), generated independently from the stoichiometric reaction of [Fp(t-BuPA)][BF₄] with TMAF. Two other plausible reaction intermediates, [Fp(t-BuPA)][BF₄] and [Fp(1-t-Bu)][BF₄], were prepared independently and structurally characterized. 2019-09-25T20:32:51Z 2019-09-25T20:32:51Z 2019-08 2019-07 2019-09-20T14:17:57Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 https://hdl.handle.net/1721.1/122286 Geeson, Michael B. et al. "Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes." Journal of the American Chemical Society 141, 34 (August 2019): 13336-13340 © 2019 American Chemical Society en http://dx.doi.org/10.1021/jacs.9b07069 Journal of the American Chemical Society Creative Commons Attribution-NonCommercial-NoDerivs License http://creativecommons.org/licenses/by-nc-nd/4.0/ application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Geeson, Michael Baily Transue, Wesley Cummins, Christopher C Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes |
| title | Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes |
| title_full | Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes |
| title_fullStr | Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes |
| title_full_unstemmed | Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes |
| title_short | Organoiron- and Fluoride-Catalyzed Phosphinidene Transfer to Styrenic Olefins in a Stereoselective Synthesis of Unprotected Phosphiranes |
| title_sort | organoiron and fluoride catalyzed phosphinidene transfer to styrenic olefins in a stereoselective synthesis of unprotected phosphiranes |
| url | https://hdl.handle.net/1721.1/122286 |
| work_keys_str_mv | AT geesonmichaelbaily organoironandfluoridecatalyzedphosphinidenetransfertostyrenicolefinsinastereoselectivesynthesisofunprotectedphosphiranes AT transuewesley organoironandfluoridecatalyzedphosphinidenetransfertostyrenicolefinsinastereoselectivesynthesisofunprotectedphosphiranes AT cumminschristopherc organoironandfluoridecatalyzedphosphinidenetransfertostyrenicolefinsinastereoselectivesynthesisofunprotectedphosphiranes |