RESUMO
A method has been developed for the introduction of nonaromatic heterocyclic structures onto aryl and heteroaryl bromides using alkyl tosylates in a reductive cross-coupling manifold. This protocol offers an improvement over previous methods by utilizing alkyl tosylate coupling partners that are bench-stable, crystalline solids that can be prepared from inexpensive, commercially available alcohols.
RESUMO
Reductive cross-coupling allows the direct C-C bond formation between two organic halides without the need for preformation of an organometallic reagent. A method has been developed for the reductive cross-coupling of nonaromatic, heterocyclic bromides with aryl or heteroaryl bromides. The developed conditions use an air-stable Ni(II) source in the presence of a diamine ligand and a metal reductant to allow late-stage incorporation of saturated heterocyclic rings onto aryl halides in a functional-group tolerant manner.
Assuntos
Brometos/química , Reagentes de Ligações Cruzadas/química , Compostos Heterocíclicos/química , Compostos Heterocíclicos/síntese química , Indicadores e Reagentes/química , Metais/química , Catálise , Ligantes , Estrutura Molecular , OxirreduçãoRESUMO
A method has been developed for the Pd-catalyzed synthesis of α-(hetero)aryl esters and amides through a Suzuki-Miyaura cross-coupling reaction. This method avoids the use of strong base, does not necessitate inert or low temperature formation of reagents, and does not require the use of a large excess of organometallic reagent. Utilization of organotrifluoroborate salts as nucleophilic partners allows a variety of functional groups and heterocyclic compounds to be tolerated.
Assuntos
Acetamidas/química , Ácidos Borônicos/química , Cloroacetatos/química , Compostos Heterocíclicos/síntese química , Indicadores e Reagentes/química , Paládio/química , Sais/química , Catálise , Ésteres , Compostos Heterocíclicos/química , Estrutura Molecular , TemperaturaRESUMO
Conditions have been developed for the reductive cross-coupling of 3-bromo-2,1-borazaronaphthalenes with primary and secondary alkyl iodides. This method allows direct alkylation of azaborine cores, providing efficient access to functionalized isosteres of naphthalene derivatives.
Assuntos
Compostos de Boro/química , Compostos de Boro/síntese química , Hidrocarbonetos Bromados/química , Hidrocarbonetos Bromados/síntese química , Hidrocarbonetos Iodados/química , Naftalenos/química , Naftalenos/síntese química , Catálise , Técnicas de Química Combinatória , Estrutura MolecularRESUMO
The synthesis of ß,γ-alkynyl esters and amides using air-stable potassium alkynyltrifluoroborates as nucleophilic partners in a mild Suzuki-Miyaura cross-coupling reaction has been achieved. Propargyl esters and amides were obtained in high yields using a low catalyst loading, and the substrate scope of the reaction has been significantly improved over previous methods.
Assuntos
Acetamidas/síntese química , Alcinos/síntese química , Boratos/química , Cloroacetatos/síntese química , Acetamidas/química , Alcinos/química , Catálise , Cloroacetatos/química , Estrutura Molecular , Paládio , Potássio , EstereoisomerismoRESUMO
A protocol for the stereocontrolled synthesis of (E)- and (Z)-ß,γ-unsaturated esters and amides is reported. 2-Chloroacetates as well as secondary and tertiary 2-chloroacetamides were successfully employed as electrophiles in the Suzuki-Miyaura cross-coupling reaction with potassium (E)- and (Z)-alkenyltrifluoroborates, affording the corresponding products in high yield.