Direct Observation and Analysis of the Halo-Amino-Nitro Alkane Functional Group.
Journal
Chem
ISSN: 2451-9294
Titre abrégé: Chem
Pays: United States
ID NLM: 101688902
Informations de publication
Date de publication:
09 May 2019
09 May 2019
Historique:
entrez:
9
8
2020
pubmed:
9
5
2019
medline:
9
5
2019
Statut:
ppublish
Résumé
Conventional amide synthesis is a mainstay in discipline-spanning applications, and it is a reaction type that historically developed as a singular paradigm when considering the carbon-nitrogen bond-forming step. Umpolung amide synthesis (UmAS) exploits the unique properties of an α-halo nitroalkane in its reaction with an amine to produce an amide. The "umpolung" moniker reflects its paradigm-breaking C-N bond formation on the basis of evidence that the nucleophilic nitronate carbon and electrophilic nitrogen engage to form a tetrahedral intermediate (TI) that is an unprecedented functional group, a 1,1,1-halo-amino-nitro alkane (HANA). Studies probing HANA transience have failed to capture this (presumably) highly reactive intermediate. We report here the direct observation of a HANA, its conversion thermally to an amide functionality, and quantitative analysis of this process using computational techniques. These findings validate the HANA as a functional group common to UmAS and diverted UmAS, opening the door to its targeted use and creative manipulation.
Identifiants
pubmed: 32766460
doi: 10.1016/j.chempr.2019.03.001
pmc: PMC7405871
mid: NIHMS1525558
doi:
Types de publication
Journal Article
Langues
eng
Pagination
1248-1264Subventions
Organisme : NIGMS NIH HHS
ID : R01 GM063557
Pays : United States
Déclaration de conflit d'intérêts
DECLARATION OF INTERESTS The authors declare no competing interests.
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