RESUMO
The introduction of an alkoxyethyl moiety onto aromatic substructures has remained a long-standing challenge for synthetic organic chemists. The main reasons are the inherent instability of alkoxyethylmetallic species and the lack of general procedures to access them. A new method utilizing a cross-coupling strategy based on the exceptional properties of organotrifluoroborates has been developed, and the method allows an easy and efficient installation of this unit on a broad range of aryl and heteroaryl bromides.
Assuntos
Boratos/química , Compostos Heterocíclicos/síntese química , Oxigênio/química , Catálise , Compostos Heterocíclicos/química , Estrutura Molecular , Potássio/químicaRESUMO
Solid-supported organotrifluoroborates were prepared in high yields by ion exchange with Amberlyst resins. The reactivity of solid supported aryltrifluoroborates was evaluated in Suzuki-Miyaura couplings with numerous aryl bromide partners. Electron-rich and -poor substituents were tolerated on both substrates, providing yields up to 90%. Examples of alkyl-, alkenyl-, alkynyl-, and heteroaryltrifluoborates were also successfully cross-coupled to aryl halides.
Assuntos
Boratos/química , Hidrocarbonetos Halogenados/química , Boratos/síntese química , Catálise , Estrutura MolecularRESUMO
Efficient Csp(3)-Csp(3) Suzuki couplings have been developed with both potassium cyclopropyl- and alkoxymethyltrifluoroborates. Moderate to good yields have been achieved in the cross-coupling of potassium cyclopropyltrifluoroborate with benzyl chlorides possessing electron-donating or electron-withdrawing substituents. Benzyl chloride was also successfully cross-coupled to potassium alkoxymethyltrifluoroborates derived from primary, secondary, and tertiary alcohols.
Assuntos
Compostos de Benzil/química , Boratos/química , Reagentes de Ligações Cruzadas/química , Ciclopropanos/química , Potássio/química , terc-Butil Álcool/análogos & derivados , terc-Butil Álcool/química , Estrutura MolecularRESUMO
A direct alkylation of various heteroaryls using stoichiometric potassium alkyl- and alkoxymethyltrifluoroborates has been developed. This method leads to the synthesis of complex substituted heterocycles, which have been obtained with yields up to 89%.
Assuntos
Álcoois/química , Boratos/química , Compostos de Flúor/química , Potássio/química , Alquilação , Radicais Livres/química , Metilação , Estrutura MolecularRESUMO
A straightforward synthesis of aminodibenzoxepines, new analogues of N-acetylcolchinol, is reported by using two different strategies. The first strategy involves a Grignard addition, a biaryl Suzuki-Miyaura coupling, and a HF-mediated cyclodehydration as key steps. A second strategy, better adapted to the synthesis of analogues bearing a benzylic substituent, was designed by inverting the order of the Grignard addition and the biaryl coupling. This allowed the rapid and reliable production of a series of substituted aminodibenzoxepines. A chelate model was proposed to account for the diastereoselectivity observed in the Grignard addition step.