DC Field | Value | Language |
---|---|---|
dc.contributor.author | Baek, Yunjung | ko |
dc.contributor.author | Das, Anuvab | ko |
dc.contributor.author | Zheng, Shao-Liang | ko |
dc.contributor.author | Reibenspies, Joseph H. | ko |
dc.contributor.author | Powers, David C. | ko |
dc.contributor.author | Betley, Theodore A. | ko |
dc.date.accessioned | 2022-04-16T06:41:52Z | - |
dc.date.available | 2022-04-16T06:41:52Z | - |
dc.date.created | 2022-04-04 | - |
dc.date.issued | 2020-06 | - |
dc.identifier.citation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.142, no.25, pp.11232 - 11243 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10203/295157 | - |
dc.description.abstract | Treatment of (L-Ar)CoBr (L-Ar = 5-mesityl-1,9-(2,4,6-Ph3C6H2)dipyrrin) with a stoichiometric amount of 1-azido-4-(tertbutyl)benzene N-3(C(6)H(4)p-Bu-t) furnished the corresponding fourcoordinate organoazide-bound complex (L-Ar)CoBr(N-3(C6H4-p-Bu-t)). Spectroscopic and structural characterization of the complex indicated redox innocent ligation of the organoazide. Slow expulsion of dinitrogen (N-2) was observed at room temperature to afford a ligand functionalized product via a [3 + 2] annulation, which can be mediated by a high-valent nitrene intermediate such as a Co-III iminyl (L-Ar)CoBr(N-center dot(C6H4-p-Bu-t)) or Co-IV imido (L-Ar)CoBr(N(C6H4-p-Bu-t)) complex. The presence of the proposed intermediate and its viability as a nitrene group transfer reagent are supported by intermolecular C-H amination and aziridination reactivities. Unlike (L-Ar)CoBr(N-3(C6H4-p-Bu-t)), a series of alkyl azide-bound Co-II analogues expel N-2 only above 60 degrees C, affording paramagnetic intermediates that convert to the corresponding Co-imine complexes via alpha-H-atom abstraction. The corresponding N-2-released structures were observed via single-crystal-to-crystal transformation, suggesting formation of a Co-nitrenoid intermediate in solid-state. Alternatively, the alkyl azide- bound congeners supported by a more sterically accessible dipyrrinato scaffold L-tBu(L-tBu = 5-mesityl-(1,9-di-tert-butyl)dipyrrin) facilitate intramolecular 1,3-dipolar cycloaddition as well as C-H amination to furnish 1,2,3-dihydrotriazole and substituted pyrrolidine products, respectively. For the C-H amination, we observe that the temperature required for azide activation varies depending on the presence of weak C-H bonds, suggesting that the alkyl azide adducts serve as viable species for C-H amination when the C-H bonds are (1) proximal to the azide moiety and (2) sufficiently weak to be activated. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.title | C-H Amination Mediated by Cobalt Organoazide Adducts and the Corresponding Cobalt Nitrenoid Intermediates | - |
dc.type | Article | - |
dc.identifier.wosid | 000543780500039 | - |
dc.identifier.scopusid | 2-s2.0-85087013724 | - |
dc.type.rims | ART | - |
dc.citation.volume | 142 | - |
dc.citation.issue | 25 | - |
dc.citation.beginningpage | 11232 | - |
dc.citation.endingpage | 11243 | - |
dc.citation.publicationname | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1021/jacs.0c04252 | - |
dc.contributor.localauthor | Baek, Yunjung | - |
dc.contributor.nonIdAuthor | Das, Anuvab | - |
dc.contributor.nonIdAuthor | Zheng, Shao-Liang | - |
dc.contributor.nonIdAuthor | Reibenspies, Joseph H. | - |
dc.contributor.nonIdAuthor | Powers, David C. | - |
dc.contributor.nonIdAuthor | Betley, Theodore A. | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | BOND AMINATION | - |
dc.subject.keywordPlus | ORGANIC AZIDES | - |
dc.subject.keywordPlus | STRUCTURAL-CHARACTERIZATION | - |
dc.subject.keywordPlus | 1,3-DIPOLAR CYCLOADDITION | - |
dc.subject.keywordPlus | IMIDOMETAL COMPLEXES | - |
dc.subject.keywordPlus | PORPHYRIN COMPLEXES | - |
dc.subject.keywordPlus | RADIATION-DAMAGE | - |
dc.subject.keywordPlus | SPECIES RELEVANT | - |
dc.subject.keywordPlus | ARYL AZIDES | - |
dc.subject.keywordPlus | AZIRIDINATION | - |
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