1,2-Carbopentafluorophenylation of Alkynes: The Metallomimetic Pull-Push Reactivity of Tris(pentafluorophenyl)borane.
Chemistry
; 27(34): 8822-8831, 2021 Jun 16.
Article
em En
| MEDLINE
| ID: mdl-33860597
ABSTRACT
We report the novel single-step 1,2-dicarbofunctionalization of an arylacetylene with an allylsilane and tris(pentafluorophenyl)borane [B(C6 F5 )3 ] involving C-C bond formation with C-H bond scission at the ß-position to the silicon atom of an allylsilane and BâC migration of a C6 F5 group. The 1,2-carbopentafluorophenylation occurs smoothly without the requirement for a catalyst or heating. Mechanistic studies suggest that the metallomimetic "pull-push" reactivity of B(C6 F5 )3 imparts consecutive electrophilic and nucleophilic characteristics to the benzylic carbon of the arylacetylene. Subsequent photochemical 6π-electrocyclization affords tetrafluoronaphthalenes, which are important in the pharmaceutical and materials sciences. Owing to the unique reactivity of B(C6 F5 )3 , the 1,2-carbopentafluorophenylation using 2-substituted furan proceeded with ring opening, and the reaction using silyl enolates formed a C-C bond with C-O bond scission at the silyloxy-substituted carbon.
Palavras-chave
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Boranos
/
Alcinos
Idioma:
En
Ano de publicação:
2021
Tipo de documento:
Article