A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[superscript V]═O Redox Cycling
A small-ring phosphacycle, 1,2,2,3,4,4-hexamethylphosphetane, is found to catalyze deoxygenative N-N bond-forming Cadogan h eterocyclization of o-nitrobenzaldimines, o-nitroazobenzenes, and related substrates in the presence of hydrosilane terminal reductant. The reaction provides a chemoselective c...
| Main Authors: | , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Published: |
American Chemical Society (ACS)
2018
|
| Online Access: | http://hdl.handle.net/1721.1/116319 https://orcid.org/0000-0002-7683-2984 https://orcid.org/0000-0003-3786-0453 |
| _version_ | 1811069289064562688 |
|---|---|
| author | Putnik, Rachel A. Nykaza, Trevor Vincent Harrison, Tyler Steven Ghosh, Avipsa Radosevich, Alexander T. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Putnik, Rachel A. Nykaza, Trevor Vincent Harrison, Tyler Steven Ghosh, Avipsa Radosevich, Alexander T. |
| author_sort | Putnik, Rachel A. |
| collection | MIT |
| description | A small-ring phosphacycle, 1,2,2,3,4,4-hexamethylphosphetane, is found to catalyze deoxygenative N-N bond-forming Cadogan h eterocyclization of o-nitrobenzaldimines, o-nitroazobenzenes, and related substrates in the presence of hydrosilane terminal reductant. The reaction provides a chemoselective catalytic synthesis of 2H-indazoles, 2H-benzotriazoles, and related fused heterocyclic systems with good functional group compatibility. On the basis of both stoichiometric and catalytic mechanistic experiments, the reaction is proposed to proceed via catalytic P[superscript III]/P[superscript V] = O cycling, where DFT modeling suggests a turnover-limiting (3+1) cheletropic addition between the phosphetane catalyst and nitroarene substrate. Strain/distortion analysis of the (3+1) transition structure highlights the controlling role of frontier orbital effects underpinning the catalytic performance of the phosphetane. |
| first_indexed | 2024-09-23T08:08:44Z |
| format | Article |
| id | mit-1721.1/116319 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T08:08:44Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1163192022-09-23T11:13:36Z A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[superscript V]═O Redox Cycling Putnik, Rachel A. Nykaza, Trevor Vincent Harrison, Tyler Steven Ghosh, Avipsa Radosevich, Alexander T. Massachusetts Institute of Technology. Department of Chemistry Nykaza, Trevor Vincent Harrison, Tyler Steven Ghosh, Avipsa Radosevich, Alexander T. A small-ring phosphacycle, 1,2,2,3,4,4-hexamethylphosphetane, is found to catalyze deoxygenative N-N bond-forming Cadogan h eterocyclization of o-nitrobenzaldimines, o-nitroazobenzenes, and related substrates in the presence of hydrosilane terminal reductant. The reaction provides a chemoselective catalytic synthesis of 2H-indazoles, 2H-benzotriazoles, and related fused heterocyclic systems with good functional group compatibility. On the basis of both stoichiometric and catalytic mechanistic experiments, the reaction is proposed to proceed via catalytic P[superscript III]/P[superscript V] = O cycling, where DFT modeling suggests a turnover-limiting (3+1) cheletropic addition between the phosphetane catalyst and nitroarene substrate. Strain/distortion analysis of the (3+1) transition structure highlights the controlling role of frontier orbital effects underpinning the catalytic performance of the phosphetane. National Institute of General Medical Sciences (U.S.) (Award GM114547) Alfred P. Sloan Foundation Amgen Inc. 2018-06-14T18:35:32Z 2018-06-14T18:35:32Z 2017-05 2018-06-13T15:01:37Z Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/116319 Nykaza, Trevor V., et al. “A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[subscript V] ═O Redox Cycling.” Journal of the American Chemical Society, vol. 139, no. 20, May 2017, pp. 6839–42. https://orcid.org/0000-0002-7683-2984 https://orcid.org/0000-0003-3786-0453 http://dx.doi.org/10.1021/JACS.7B03260 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) PMC |
| spellingShingle | Putnik, Rachel A. Nykaza, Trevor Vincent Harrison, Tyler Steven Ghosh, Avipsa Radosevich, Alexander T. A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[superscript V]═O Redox Cycling |
| title | A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[superscript V]═O Redox Cycling |
| title_full | A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[superscript V]═O Redox Cycling |
| title_fullStr | A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[superscript V]═O Redox Cycling |
| title_full_unstemmed | A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[superscript V]═O Redox Cycling |
| title_short | A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[superscript V]═O Redox Cycling |
| title_sort | biphilic phosphetane catalyzes n n bond forming cadogan heterocyclization via p superscript iii p superscript v ═o redox cycling |
| url | http://hdl.handle.net/1721.1/116319 https://orcid.org/0000-0002-7683-2984 https://orcid.org/0000-0003-3786-0453 |
| work_keys_str_mv | AT putnikrachela abiphilicphosphetanecatalyzesnnbondformingcadoganheterocyclizationviapsuperscriptiiipsuperscriptvoredoxcycling AT nykazatrevorvincent abiphilicphosphetanecatalyzesnnbondformingcadoganheterocyclizationviapsuperscriptiiipsuperscriptvoredoxcycling AT harrisontylersteven abiphilicphosphetanecatalyzesnnbondformingcadoganheterocyclizationviapsuperscriptiiipsuperscriptvoredoxcycling AT ghoshavipsa abiphilicphosphetanecatalyzesnnbondformingcadoganheterocyclizationviapsuperscriptiiipsuperscriptvoredoxcycling AT radosevichalexandert abiphilicphosphetanecatalyzesnnbondformingcadoganheterocyclizationviapsuperscriptiiipsuperscriptvoredoxcycling AT putnikrachela biphilicphosphetanecatalyzesnnbondformingcadoganheterocyclizationviapsuperscriptiiipsuperscriptvoredoxcycling AT nykazatrevorvincent biphilicphosphetanecatalyzesnnbondformingcadoganheterocyclizationviapsuperscriptiiipsuperscriptvoredoxcycling AT harrisontylersteven biphilicphosphetanecatalyzesnnbondformingcadoganheterocyclizationviapsuperscriptiiipsuperscriptvoredoxcycling AT ghoshavipsa biphilicphosphetanecatalyzesnnbondformingcadoganheterocyclizationviapsuperscriptiiipsuperscriptvoredoxcycling AT radosevichalexandert biphilicphosphetanecatalyzesnnbondformingcadoganheterocyclizationviapsuperscriptiiipsuperscriptvoredoxcycling |