| dc.contributor |
Massachusetts Institute of Technology. Department of Chemistry |
|
| dc.contributor |
Nykaza, Trevor Vincent |
|
| dc.contributor |
Harrison, Tyler Steven |
|
| dc.contributor |
Ghosh, Avipsa |
|
| dc.contributor |
Radosevich, Alexander T. |
|
| dc.creator |
Putnik, Rachel A. |
|
| dc.creator |
Nykaza, Trevor Vincent |
|
| dc.creator |
Harrison, Tyler Steven |
|
| dc.creator |
Ghosh, Avipsa |
|
| dc.creator |
Radosevich, Alexander T. |
|
| dc.date |
2018-06-14T18:35:32Z |
|
| dc.date |
2018-06-14T18:35:32Z |
|
| dc.date |
2017-05 |
|
| dc.date |
2018-06-13T15:01:37Z |
|
| dc.date.accessioned |
2023-03-01T17:57:11Z |
|
| dc.date.available |
2023-03-01T17:57:11Z |
|
| dc.identifier |
0002-7863 |
|
| dc.identifier |
1520-5126 |
|
| dc.identifier |
http://hdl.handle.net/1721.1/116319 |
|
| dc.identifier |
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. |
|
| dc.identifier |
https://orcid.org/0000-0002-7683-2984 |
|
| dc.identifier |
https://orcid.org/0000-0003-3786-0453 |
|
| dc.identifier.uri |
http://localhost:8080/xmlui/handle/CUHPOERS/278186 |
|
| dc.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. |
|
| dc.description |
National Institute of General Medical Sciences (U.S.) (Award GM114547) |
|
| dc.description |
Alfred P. Sloan Foundation |
|
| dc.description |
Amgen Inc. |
|
| dc.format |
application/pdf |
|
| dc.publisher |
American Chemical Society (ACS) |
|
| dc.relation |
http://dx.doi.org/10.1021/JACS.7B03260 |
|
| dc.relation |
Journal of the American Chemical Society |
|
| dc.rights |
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. |
|
| dc.source |
PMC |
|
| dc.title |
A Biphilic Phosphetane Catalyzes N–N Bond-Forming Cadogan Heterocyclization via P[superscript III]/P[superscript V]═O Redox Cycling |
|
| dc.type |
Article |
|
| dc.type |
http://purl.org/eprint/type/JournalArticle |
|